WO2006136191A1 - Triethanolamine perchlorato (triflato) metal inner complex coordination polymers as additives for synthetic polymers - Google Patents

Abstract

Disclosed is a stabilizer system for chlorine-containing polymers, particularly PVC, comprising at least one coordination polymeric triethanolamine perchlorato(triflato) metal inner complex containing a monomer unit of formula (A). Said stabilizer system can additionally contain substituted cyanoacetyl ureas or/and 6-aminouracils or/and 3-aminocrotonic ester or/and hydantoins or/and monomeric or polymeric dihydropyridines or alkaline earth hydroxides or/and hydrotalcites or/and dawsonites or/and zeolites or/and glycidyl compounds or/and cyanamides or/and cyanoguanidines or/and melamines. Phosphites or/and sterically hindered amines or/and NOR-HALS compounds can also be provided.

Description

 Coordination polymers Triethanolamine perchlorato (triflato) metal core complexes as additives for synthetic polymers

The present invention relates to compositions of synthetic polymers and coordination polymers TriethanolammpercWorato (triflato) -Metall-Irmerkornplexen and stabilizer containing the inner complexes. Furthermore, the invention relates to selected inner complexes and their preparation.

It is known that halogen-containing plastics or molding compositions prepared therefrom are prone to degradation or decomposition reactions when exposed to thermal stress or coming into contact with high-energy radiation, for example ultraviolet light.

To stabilize e.g. PVC prior to processing hitherto used in practice heavy metal-containing stabilizers based on Cd, Pb, Sn and Zn or less toxicologically less hazardous metals, such as barium. In these cases, the already detrimental effect - in view of improved resorbability and tolerability in the warm-blooded organism - by conversion into fatty acid-based organic metal compounds, e.g. Laurate, stearates and oleates, or by transformation into organoderivatives (organometallic compounds or organometallic compounds), in particular tin, additionally increased. Especially in the latter case, the alkylation of the metal to form a, even under metabolic conditions, hydrolysis-stable metal carbon bond an enteric system is created which has capabilities to overcome the blood-brain barrier to develop any neurotoxic potential.

This problem affects not only the users of finished PVC articles, but also their manufacturers who incorporate such heavy metal stabilizers in the PVC substrate. Also affected are the producers of these stabilizers themselves, which convert heavy metal-containing precursors into just these stabilizers.

In addition to the toxic effect on the warm-blooded organism, these metals and their (organic) compounds or organo compounds "Ökotoxwirkung", ie a harmful effects on fish, crabs and other marine and freshwater organisms; See List of Priority Hazardous Substances, adopted at the Third North Sea Conference (The Hague, 3/1990), which lists zinc in addition to lead, cadmium, arsenic and mercury, see also Directive 2000/60 / EC (definition the list of priority substances in the field of water policy - latest update 11/2001) and the Progress Report of the Fifth North Sea Conference (Bergen, 3/2002), which notes that, among other things, the target values for zinc were not met. Furthermore, in the Sewage Sludge Ordinance of the Federal Environmental Agency (BGBl. I p. 1492, last update v. 25.04.2002) maximum levels are set for heavy metals, namely Pb, Cd, Cr, Cu ₅ Ni, Hg and Zn. Also, inorganic heavy metal salts can be converted to highly toxic neurotoxic compounds via the naturally occurring mechanism of biomethylation. In particular trimethyl lead and trimethyltin compounds should be considered here. Organic stabilizers based on the elements C, H, N, O are converted during waste incineration into CO ₂ , H ₂ O and ammonium compounds, all of which are biocompatible. Heavy metal compounds, on the other hand, are not degraded, so they are persistent and bioaccumulate.

The substitution of heavy metal-containing stabilizers by organic compounds should therefore be an important contribution to this goal achievement. In the UK and Denmark, the use of Pb stabilizers in PVC drinking water pipes was banned at the end of 2002 and 2003, respectively. In Denmark, this ban is also linked to the requirement to use no Sn stabilizers instead of Pb. Other countries, such as Sweden, Norway or Finland, want to follow this ban. A Pb ban across the EU is currently under negotiation with the competent authorities.

There is therefore a need for organic ("green") stabilizers which are free from heavy metal compounds or other toxicologically objectionable metal compounds, in particular completely free of lead, tin and barium.

Alkali or Erdalkaliperchloratsalze in the presence of metal soaps are long known costabilizers for plasticized PVC, especially in the automotive sector, this addition should retard the PVC discoloration in PUR-backfoamed moldings (JP 59184240, JP 6219732, JP 03097748, US 4957954 EP 273766 A, JP 03126745). Later, it was found that the addition of inorganic perchlorate salts leads to an improvement in the effectiveness of organically stabilized (heavy metal-free = Zn and Pb-fiei) rigid PVC (EP 768336 A2).

Another inorganic perchlorate salt-containing stabilizer is also known from Japan. This is an anion-modified hydrotalcite. It is also mainly used in soft PVC (EP 522810 A2).

Recently, two applications have appeared which describe replacing inorganic perchlorate salts by onium, especially ammonium perchlorate salts (DE 10160662 A1, DE 10214152 A1). Two more applications for PVC applications are also from Japan; they contain u. a. also the triethanolammonium (TEA) perchlorate (JP 61009451) or surface-active trialkylethanolammonium perchlorates (JP 1090242), which can be used as antistatic agents. There is also a larger group of Japanese patents claiming surfactant tetraalkylammonium perchlorates as antistatic components in PVC. Also worth mentioning in this connection is DE 2540655 A and the publication by S. RIETHMAYER in Rubber, Asbestos, Plastics (GAK), [A], 298-308 (1973).

A further modification (on an inorganic basis) of alkali metal perchlorate salts is accomplished by addition of calcium hydroxide (DE 10124734 A1). This dry mixture is obtained by an "in situ" process from aqueous perchlorate salt solution and quicklime.

It is also known to mix melamine and hydantoin with perchlorate salts and to use these mixtures as PVC thermal stabilizers (JP 53016750). The examples mentioned there, however, mostly use large amounts of plasticizer or immense amounts of calcium stearate or large amounts of inorganic fillers. For the stabilization of rigid PVC, these systems are unsuitable.

It is also known to complex primary alkanolamines with zinc glutamate or sulfate. In addition, EP 394547 A2 describes stabilizer systems for PVC which contain liquid alkali metal or alkaline earth metal perchlorate complexes with polyols as components. N-containing polyols as complex ligands and complexes in solid form are not claimed. It is also known alkanolamines together with perchlorate salts to use as PVC thermal stabilizers (WO 02/48249). Fixed solutions (solid solutions) or complexes or even inner complexes are not described there. Furthermore, solutions of metal perchlorate salts in glycols or glycol ethers are claimed as stabilizer components (WO 94/24200). In addition, absorbates of alkali or Erdalkaliperchloraten on zeolites or calcium silicate in patents are described several times, as in EP 768336 A2 and US 5034443 and in US 5225108. However, these are mentioned in EP 1404756 Al specifically as stabilizer components.

All these publications are characterized by further numerous disadvantages:

1. Almost all inorganic perchlorate salts melt above 250 ° C usually above 300 ° C and then with decomposition. They are therefore difficult to disperse homogeneously in the polymer substrate and difficult aufschließbar. In addition, they often form specks and inclusions in the finished molded article due to their grain. Fine grinding of the perchlorate salts, which could provide relief, is technologically difficult to carry out.

2. Inorganic perchlorate salts are in most cases hygroscopic and cake or agglomerate during storage. This is shown by the fact that magnesium perchlorate is even used as a desiccant.

3. Inorganic perchlorate salts on carriers, such as calcium silicate or zeolites, are not universally applicable. Transparent rigid PVC products can not be produced with these additives.

4. Aqueous solutions or solutions of these salts in an organic solvent can in principle be used, but on the one hand water in the stabilizer system leads to incompatibility and interreaction in the polymer and to bubble formation. On the other hand, the addition of organic solvents in hard PVC leads to a lowering of the Vicat value (80 ° C) and to volatile organic vapors (VOC problem) during extrusion and calendering.

5. Certain organic perchlorate salts, namely primary, secondary and tertiary amine perchlorates, are dangerous to handle as NH perchlorates due to their tendency to spontaneously decompose, with ammonium perchlorate being used as the last member of this series even as a rocket fuel component. Furthermore, amine perchlorates are not optimal in terms of their melting points. quaternary Ammonium perchlorates are not previously described as thermal stabilizers for PVC, but as such have only a modest performance.

6. The amines on which the amine perchlorates are based are generally highly degradative in PVC (e.g., nicotinic acid ester, formamide and trioctylamine).

Quaternary ammonium perchlorates which have been proposed as PVC antistatic agents and whose thermostabilizing effect is mentioned in PVC are to be regarded with skepticism, since it has been found that this class of compounds has a thermodegrading effect in PVC.

The object of the present invention is therefore to provide compositions and stabilizer systems which at least partially overcome the disadvantages of the prior art.

The object has been achieved by a composition comprising at least one synthetic polymer and at least one coordination-polymer triethanolamine perchlorato (triflato) metal inner complex having the monomer unit of the formula (A):

(A)

in which

Mt = Li, Na, K, Mg, Ca, Sr, Ba and Zn;

An = OClO ₃ or OS (O ₂ ) CF ₃ and

q = 1 or 2. Furthermore, the object has been achieved by a stabilizer system for synthetic polymers containing a coordination polymer triethanolamine perchlorato (triflato) - metal-inner complex with the monomer unit of the formula (A):

(A)

in which

Mt = Li, Na, K ₅ Mg ₅ Ca ₅ Sr, Ba and Zn;

An = OClO ₃ or OS (O ₂ ) CF ₃ and

q = 1 or 2

It has been found that the inner complexes (A) according to the invention ₅ at least partially do not have the disadvantages described in points 1-6. Thus, the new compounds often show a sharp Mp, then melt usually lower and without decomposition. The melting points are higher than 8O ⁰ C, but usually below 20O ⁰ C ₅ ie they do not adversely affect the Vicat (80 ° C) value of the finished molding and melt homogeneously at the processing temperatures, whereby a speckling and a Festpartikelneinschluß is avoided. Transparent PVC articles can thus be produced. Homogeneous product distribution is guaranteed during hot mixing. The powder blends are non-sticky, non-caking, non-agglomerating and free-flowing due to their lack of hygroscopicity. The products can be stored without sacrificing quality in air. The solids do not have sharp-edged crystallites, so they are not abrasive during processing. By incorporation into a stable cage structure (metallate cage or aza-cage), the perchlorate group is phlegmatized. The thermostabilizing effect of these inner complexes, especially in the form of two-and-three combinations with initial color improvers (AFV), and hydrogen chloride scavenger (SCV) is significantly increased over that mentioned in the prior art (SdT). These product properties were surprising. Perchlorato-TEA-inner complexes (TEA = triethanolamine) of lithium, sodium, strontium and barium are described in JG VERKADE et al., Inorg. Chem. 33, 2137 (1994). For some of these inner complexes, an X-ray structure analysis (RSA) was also performed. For the sodium and barium inner complexes, the stoichiometry is as follows: [(TEA) NaOClO ₃ J _n and [(TEA) ₂ Ba (0C10 ₃ ) ₂ ] ₂ , the degree of oligo- or polymerization being evident from the RSA. The inner complexes are anhydrous. In the case of the sodium inner complex ^ with the melting point of 129-130 ° C, the RSA shows the following picture: the Na cation has four ligands in the coordination sphere, one TEA group acts as a tetradentate, non-bridging KN O ligand, two bridging, non-chelating TEA groups (μ-ligands) and a monodentate-binding perchlorate anion. This results in an overall coordination number of seven for sodium. Since the perchlorate anion acts as a perchlorato ligand, these substances belong to the class of inner complex compounds. Surprisingly, such internal complexes are useful in stabilizer systems for synthetic polymers and in compositions with these. Preferably, the synthetic polymer is a halogen-containing polymer, especially PVC. Due to its particular suitability for halogen-containing polymers, reference will be made hereinafter to the description of the invention. It should be emphasized, however, that non-halogen-containing synthetic polymers can also be stabilized in the context of the present invention. The suitability of such a complex structure is also surprising since the state of the art (DSVAN ES in Catalytic Heat Stabilizers: Fact or Fiction - 9th International PVC Conf., Brighton, Apr. 2005) states that perchlorate salts are only effective in PVC stabilize when a "naked" Perchloratanion and thus also a "naked" metal cation exist. This is to be equated with a non-coordinating perchlorate anion and a non-coordinating metal cation, which in turn can not be reconciled with the described structural features of (A). All compounds according to the invention are solids and contain TEA as tertiary alkanolamine as complex ligand.

^ι) abbreviated in this PS font with TEAP. Furthermore, it was surprising that this particular ligand property of TEA, since the introduction of additional methyl groups (transition from the tertiary alkanolamine TEA to the tertiary alkanolamine TIPA), altered this complexing feature to fail an attempt to prepare and isolate solid homologous TIPA complexes. Equally impossible is the introduction of a single methyl group or a long-chain (surfactant) residue in the TEA ligands, since here too the stable inner complex (cage) structure is disturbed.

Another object of the present invention are inner complexes of formula (A), as indicated above, wherein Mt = Li, Na or Ca; q is 1 or 2 and An is OClO ₃ or OS (O ₂ ) CF ₃ ; preferably, Mt = Li, Na; q = 1 and An = OClO ₃ .

Another object of the present invention are inner complexes in which Mt =

Ca and q = 2.

The following inner complexes are listed (using the following abbreviations: perchlorato = Pc and triflato = Tf),

[(TEA) NaPc] [A-I], [(TEA) NaTf] [A-2], [(TEA) LiPc] [A-3], [(TEA) LiTfJ [A-4],

[(TEA) KPc] [A-5], [(TEA) KTf] [A-6], [(TEA) ₂ Mg (Pc) ₂ ] [A-7], [(TEA) ₂ Mg (Tf) ₂ ] [A-8], [(TEA) ₂ Ca (Pc) ₂ ] [A-9], [(TEA) ₂ Ca (Tf) ₂ ] [A-IO], [(TEA) ₂ Sr (Pc ) ₂ ] [A-II],

[(TEA) ₂ Sr (Tf) 2] [A 12], [(TEA) ₂ Zn (Pc) _2] [A-13], [(TEA) ₂ (ZnATf) _2] [A 14],

[(TEA) ₂ Ba (Pc) ₂ ] [A-15], [(TEA) ₂ Ba (Tf) ₂ ], [A- 16].

The inner complexes (A) according to the invention are preferably used advantageously in the halogen-containing polymer from 0.001 to 5 phr, preferably from 0.01 to 3 phr and very particularly from 0.01 to 2 phr.

The inner complexes (A) can be combined with other substance groups as follows:

Linear or cycloureid and / or polyaminocrotonic acid esters and / or cyanamides of the formulas (BI) and (B-2) and / or dihydropyridines of the formulas (CI) and (C-2):

(B-I) and (B-2) as well

and

mit

With

X = O or S; Y = CH ₂ CN, Z = H or Y and Z form the bridge member CH ₂ -C = NH,

R ¹ , R ² independently of one another = H, C ₁ -C ₂₂ -alkyl, cyclohexyl, (meth) allyl, oleyl, phenyl, benzyl, phenethyl, (tetrahydro) naphthyl, meth (or eth) oxypropyl (or ethyl), CH ₂ -CHOH-R ¹³ , CH ₂ -CHOH-CH ₂ X ¹ R ¹³ ;

X '= O or S;

R ^la is H, C _1-22 alkyl, cyclohexyl, (meth) allyl, oleyl, phenyl, benzyl, phenethyl, (tetrahydro) naphthyl or meth (or eth) oxypropyl (or ethyl); R ³ = unbranched or branched C ₂ -C ₂₀ -alkylene, which may be interrupted by 1 to 4 O or S atoms and / or substituted by 1 to 4 OH groups, or dimethylol-cyclohexane-l, 4-diyl , Polyethylene (or -propylene) glycol-α, ω-diyl (preferably, poly = tetra to deca), polyglyceryl-α, ω-diyl (preferably, poly = tetra to deca) or glycerol-triyl, trimethylolethane (or -propane) ) triyl, pentaerythritol tri (or tetra) yl, bis-trimethylolethane (or propane) tri (or tetra) yl, diglycerol tri (or tetra) yl, tetrit tetrayl, triglycerol tri (or tetra, penta) yl, pentitol pentyl, dipentaerythritol penta (or hexa) yl and hexitol hexyl;

n = 2, 3, 4, 5 or 6;

R ⁵ = H or (C ₃ - Qo-alkylidene) ^; which alkylidene may be interrupted by up to 2 O atoms or may have up to 2 substituents independently selected from the group consisting of OH, phenyl and hydroxyphenyl;

R ⁶ = H, hydroxy-C ₂ -C ₄ -alkyl, 3-C ₁ -C ₁₀ -alkoxy-2-hydroxypropyl or mono- to trihydroxy-, mono- to tri-C ₁ -C ₄ -alkyl- or / and mono- to tri-C ₁ -C ₄ alkoxyphenyl, allyl, mono- to trisubstituted phenyl;

R ⁷ , R ^{7 are} independently branched and unbranched C ₁ - C ₄ alkyl, phenyl, cyclohexyl;

W = CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CO ₂ ¹¹ C ₁₂ H ₂₅ or CO ₂ C ₂ H ₄ -S- ¹¹ C ₁₂ H ₂₅ ;

L, T = unsubstituted Ci is ₁₂ alkyl; such as

m and n 'are integers from 0 to 20

k is O or 1; and

R and R "are independently ethylene, propylene, butylene, or an alkylene or cycloalkylene bismethylene group of the type - (C _p H _2p -X-) _t C _p H _2p - where p is an integer from 2 to 8, t is one is integer from 0 to 10 and X is oxygen or sulfur. The radicals indicated in parentheses are further alternative radicals, so polyethylene (or propylene) glycol means polyethylene glycol or polypropylene glycol. This also applies below.

Equally surprising was the finding that the combination of internal complexes (A) with aminocrotonates or dihydropyridines (B-2, C-I, C-2) improves the transparency behavior. Thus, transparency levels of more than 90% can be achieved when using otherwise transparent formulation components.

Preferred definitions of the substituents, short formulas and indices are the following:

For (BI), X = O or S in all cases. Y = CH ₂ CN and Z = H for linear acidides. In the case of 6 (4) -miniobarbituric acids for cycloureids, the bridge member is YZ = CH ₂ -C = NH In the case of the aminouracils, the bridge member YZ = CR ⁵ = C-NHR ⁶ and in the case of the hydantoins, the bridge member YZ = R ¹ R ² C. For (B-2), for n = 2,3,4,5 or 6.

The substituents R ¹ and R ² may be C ₁ -C ₂₂ -alkyl, namely methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,

Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,

Heneicosyl and docosyl, which radicals may be branched or unbranched.

Preference is given to C ₁ -C ₈ -alkyl, particular preference being given to methyl, ethyl, propyl and butyl. Furthermore, R and R may be cyclohexyl, (meth) allyl, oleyl, phenyl, benzyl, phenethyl, methoxyethyl, ethoxyethyl, methoxypropyl and ethoxypropyl. Preferred are AlyI and phenethyl, cyclohexyl, benzyl, methoxypropyl and ethoxypropyl, particularly preferred are cyclohexyl, benzyl, methoxypropyl and ethoxypropyl.

Preferably, X = O and are particularly preferred R ¹ = CH ₃ and R ² = CH ₂ -CHOH-R ^la wherein R ^la preferably = H, CH _3, C ₂ H ₅ or R ² = CH ₂ -CHOH-CH ₂ oR ^13, wherein R ^la preferably = H or C ₁ - C ₁₀ alkyl and Ahyi.

C ₁ -C 10 -alkyl contains, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, Decyl, neodecyl. R ⁵ is hydrogen or (C ₃ -Qo-alkylideneh _/ 2 - the index ¹ A says that these are bis-products, that is to say alkylidene-bis-6-aminouracils The alkylidene groups mentioned are ethylidene, propylidene Butylidene, pentylidene, hexylidene, heptylidene, octylidene, nonylidene and decylidene, as well as salicylidene and cinnamylidene The term applies to linear and branched representatives Propylidene, hexylidene, heptylidene and octylidene are preferred, hexylidene and heptylidene are particularly preferred.

The substituent R ⁶ designates hydrogen and hydroxy-C ₂ -C ₄ -alkyl. The latter group contains 2-hydroxyethyl, 2- and 3-hydroxypropyl as well as 2-, 3- and 4-hydroxybutyl. Preference is given to 2-hydroxyethyl and also 2- and 3-hydroxypropyl. Particularly preferred is hydrogen.

Furthermore, for R ^6, allyl or 3-C ₁ -C ₁₀ -alkoxy-2-hydroxypropyl. These include 3-methoxy, 3-ethoxy, 3-propoxy, 3-butoxy, 3-pentoxy, 3-hexoxy, 3-heptoxy, 3-octoxy, 3-nonoxy and 3-decoxy -2-hydroxypropyl. Preferred are allyloxy, 3-butoxy, 3-octoxy and 3-decoxy-2-hydroxypropyl.

For the substituent R ^{6 also} applies mono- to trisubstituted phenyl, wherein the substituents may be hydroxy, and / or Ci - C ₄ alkyl or / and C ₁ - C ₄ alkoxy and the combination of hydroxy with methyl, ethyl, propyl and Butyl and hydroxy with

Methoxy, ethoxy, propoxy and butoxy. Preferably, the hydroxy, methyl, butyl,

Methoxy and ethoxy radical as a substituent. Particularly preferred is the hydroxy and

Methoxy group. Preference is given to mono- and disubstitution. But especially preferred is the mono-substitution. Particularly preferred are also in the

Multiple substitution the combinations hydroxy with meth (eth) oxy or hydroxy with

Monomethyl or dimethyl and the combinations of methyl, ethyl, propyl and

Butyl with methoxy, ethoxy, propoxy and butoxy. Specific examples are: 2-, 3- and 4-

hydroxyphenyl; 2-hydroxy-4-methylphenyl; 2-hydroxy-5-methylphenyl; 2-hydroxy-5-t-butylphenyl; and 2-, 3- and 4-meth (eth) oxyphenyl.

The compounds (BI) may also be present as hydrates. This is preferably the case, for Y and Z CR ⁵ = C-NR ⁶ ; particularly preferably when R ¹ or / and R ² ≠ methyl. The hydrates can be present for example as hemi-, sesqui- or dihydrate. High-melting cycloureids (mp:> 180 ° C) are preferably used in micronized form (particle size <50 microns). For (B-2) containing R ³ as C ₂ - C ₂ o-alkylene, which may be interrupted by 1 to 4 O or S atoms and / or substituted by 1 to 4 OH groups, is preferably Ethandiyl-1 , 2, propanediyl-1,2-propanediyl-1,3, butanediyl-2,3, butanediyl-1,4, CH ₂ CH ₂ OCH ₂ CH ₂₁ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂₁ CH ₂ CH ₂ SCH ₂ CH ₂ ,

CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ ,, CH ₂ CH ₂ SCH ₂ CH ₂ SCH ₂ CH ₂ , C ₃ H ₆ OC ₃ H ₆ , C ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆ C ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆ OC ₃ H ₆

CH ₂ CHOHCH ₂ OCH ₂ CHOHCH ₂ CHOHCH ₂ OCH ₂ CHOHCH ₂ OCH ₂ CHOHCH ₂ Particularly preferred are CH ₂ CH ₂ CH ₂ CH ₂ and CH ₂ CH ₂ SCH ₂ CH ₂ . Tetrite is preferably erythritol, arabinitol and xylitol, hexitol is preferably mannitol and sorbitol.

Preferred representatives of the individual substance groups are listed below. The naming is not limiting but selective.

(BI) - linear acylureas (linear cereals, acyl carbamides, acyl ureas) such as [1] N ₅ N'-dimethyl-, [2] N, N'-diethyl-, [3] N, N'-dipropyl-, [ 4] N, N'-diallyl, [5] N, N'-dibutyl, [6] N, N'-dioctyl [7] N, N'-didodecyl, and [8] N, N'- Dibenzylcyanacetureid. [9] N- or N'-monomethyl-, [10] N- or N'-monoethyl-, [11] N- or N'-monopropyl-, [12] N- or N'-monoallyl-, [13 ] N- or N'-monobutyl, [14] N or N'-monopentyl, [15] N or N'-monohexyl, [16] N or N'-monoheptyl and [17] N - or N'-monooctyl, [18] N, N'-monocyclohexyl [19] N, N'-monobenzyl and [20] N, N'-Monophenylcyanacetureid. Preference is given to [I] ₅ [2], [3], [4], [5], [8], [9], [10], [11], [12], [13], [18], [19] and [20]. Particularly preferred are [1], [4], [8], [12], [18], [19] and [20]. Very particular preference is [I].

(Bl) cycloacylureas (cyclourides, 6 (4) -iminobarbituric acids or 6-iminohydrouracils or 6-imino-dihydro-p-pyrimidinediones-2,4) as [21] (CAS No. 17743 -04-3) N , N'-dimethyl, [22] N, N'-diethyl, [23] N, N'-dipropyl, [24] N, N'-diallyl, [25] N, N'-dibutyl , [26] N, N'-dioctyl and [27] N, N'-didodecyl, [28] N, N'-dibenzyl-6 (4) -iminobarbituric acid. [29] (CAS No.17743-03-2 and 17743-02-1) N- or N'-monomethyl-, [30] N- or N'-monoethyl-, [31] N- or N'- Monopropyl, [32] N or N'-monoallyl, [33] N or N'-monobutyl, [34] N or N'-monopentyl, [35] N or N'-monohexyl , [36] N- or N'-monoheptyl- [37] N- or N'-monooctyl-, [38] N or N'-monocyclohexyl- or [39] N or N'-monophenyl- and [40] N , N'-monobenzyl-6 (4) -Iminobarbitursäure. Preferred are [21], [22], [23], [24], [25], [28], [29], [30], [31], [32], [33], [37], [ 38], [39] and [40]. Particularly preferred are [21], [24], [28], [32], [37], [38], [39] and [40]. Very particularly preferred is [21].

(BI) - cycloacylureides (aminouracils or aminopyrimidinediones-2,4) such as [41] N, N'-dimethyl, [42] N, N'-diethyl, [43] N ₅ N'-dipropyl, [44] N, N'-diallyl-, [45] N, N'-

Dibutyl, [46] N, N'-dioctyl and [47] N, N'-didodecyl, [48] N, N'-dibenzyl

Aminouracil. [49] N- or N'-monomethyl-, [50] N- or N'-monoethyl-, [51] N- or

N'-mono-propyl, [52] N or N'-monoallyl, [53] N or N'-monobutyl, [54] N or

N'-monopentyl, [55] N or N'-monohexyl, [56] N or N'-monoheptyl, [57] N or N'-monooctyl, [58] N or N ' - monocyclohexyl,

[59] N or N'-monobenzyl and [60] N or N'-monophenyl-aminouracil. Preferred are [41], [42], [43], [44], [45], [48], [49], [50], [51], [52], [53], [57], [58], [59] and [60]. Particularly preferred are [41], [44], [48], [52], [57], [58], [59] and [60]. Very particularly preferred is [41].

Preferred hydrates are the hemi- and monohydrates of [42], [43], [44] and [45].

Also included in this category are the 6-aminouracils substituted on the exocyclic N atom, such as hydroxyethylamino and hydroxypropylamino derivatives or hydroxyanilino, methoxyanilino and ethoxyanilinouracils. Furthermore, mention may be made of [61,62,63] N-2 -, - 3-and 4-hydroxyphenyl-1,3-dimethyl-6-aminouracil and [64] N-2-hydroxy-4-methylphenyl- [65 ] N-2-hydroxy-5-methylphenyl, [65] N-2-hydroxy-5-t-butylphenyl, [66,67,68] N-2, 3-and 4-methoxyphenyl, [69,70,71] N-2 -, - 3- and -4-ethoxyphenyl-1,3-dimethyl-6-aminouracil, [72] N-2-hydroxyethylamino, [73] N-2-hydroxypropylamino , [74] N-3-hydroxypropylamino, [75] N-2-hydroxybutylamino, [76] N-3-hydroxybutylamino and [77] N-4-hydroxybutylamino-1,3-dimethyl-6-aminouracil. Preferred are [61], [64], [65], [66], [69], [72], [73] and [74]. Particularly preferred are [61], [64], [65], [66] and [69]. Most preferred are [61], [66] and [69]. Also to be mentioned here are 5-substituted-6-aminouracils such as alkylidene-bis-6-aniourouracils. Mentioned [78] are 5-ethylidene, [79] 5-propylidene, [80] 5- (2-ethyl-butylidene), [81] 5-hexylidene, [82] 5-heptylidene, [83 ] 5-octylidene, [84] 5-benzylidene, [85] 5-salicylidene, [86] 5- (3-hydroxy) -benzylidene, [87] 5- (4-hydroxy) -benzylidene and [88] 5- (2-hydroxy) -3-methoxy) benzylidene and [89] 5-pentylidene bis-1,3-dimethyl-6-aminoouracil. Preferred are [80], [81], [82], [83] and [89]. Particularly preferred are [81], [82], [83] and [89]. Most preferred are [81] and [82].

Reaction of N-monosubstituted 6-aminouracils with C-glycidyl compounds and glycidyl (thio) ethers or esters gives N, N'-disubstituted

6-aminouracils. Specifically, mention may be made of: [90] 1-methyl-3- (3-isopropoxy-2-hydroxypropyl), [91] 1-phenyl-3- (3-isopropoxy-2-hydroxypropyl) -, [92] 1-methyl- 3- (3-tert-butoxy-2-hydroxypropyl) -, [93] 1-benzyl-3- (3-isopropoxy-2-hydroxypropyl) -, [94] 1

Methyl 3- (3-neononyl-carboxy-2-hydroxypropyl) -, [95] 1-methyl-3- (2-hydroxypropyl) -, [96] 1-methyl-3- (3- (2-ethylhexoxy) 2-hydroxypropyl) - ₃ [97] 1-methyl-3- (2-hydroxyhexyl), [98] 1-benzyl (2-hydroxypropyl) -, [99] 1-methyl- (2-hydroxybutyl) -

, [100] 1-benzyl- (2-hydroxybutyl) -, [101] 1-benzyl- (3-isopropoxy-2-hydroxypropyl) -,

[102] 1-methyl-3- (2-hydroxyethyl) - and [103] 1-methyl-3- (3-allyloxy-2-hydroxypropyl) -

6-aminouracil. Preferred are [90], [92], [94], [95], [96], [97], [99], [102] and [103]. Particularly preferred are [90], [92], [95], [99], and [103]. Very particularly preferred are

[95], [99], and [103].

Certain aminouracils are available in the chemicals trade: [1], [9] and [41] are "commodities" and are used as "bulk" chemicals in the technical caffeine or theobromine synthesis. Relevant literature syntheses are available for 6 (4) -iminobarbituric acids.

(BI) - hydantoins (imidazolidinediones), hydantoin [103a], 2-thiohydantoin [103b], 5-methylhydantoin [103c], 5-phenylhydantoin [103d], 5-methyl-2-thiohydantoin [103e], 5-phenyl 2-thiohyantoin [103f], 5,5-dimethylhydantoin [103g], 5,5-dimethyl-2-thiohydantoin [103h], 5-methyl-5-phenylhydantoin [103i] and 5-methyl-5-phenyl-2- thiohydantoin [103j]. Preferred are [103a] and [103b]. Very particular preference is [103a].

(B-2) Bis-aminocrotonic acid esters of [104] ethylene and [105] propylene glycol as well as of polyethylene and polypropylene glycols and of [106] glycerol and polyglycerols. Tris-aminocrotonic acid ester of [107] glycerol, [108,109] trimethylolethane (propane), [110] triethylol isocyanurate. Tetrakis aminocrotonic acid ester of [111] pentaerythritol, [112,113] bis-trimethylolethane (propane), hexakis-aminocrotonic acid ester of [114] dipentaerythritol and [115] sorbitol, and [116] butanediyl-1,4- and [117] thio-bis ethanediyl aminocrotonate. Preferred are [104], [105], [108], [109], [111], [113], [116] and [117].

Particularly preferred are [104], [105], [116] and [117]. Very particularly preferred are [116] and [117]. Both compounds are produced on an industrial scale.

(C-I) Monomeric dihydropyridines, such as dimethyl-dihydropyridine dicarboxylic acid methyl ester [118], bis-dicarboxylic acid ethyl ester [119] and dicarboxylic acid dilauryl ester [120] (a compound that is produced on an industrial scale).

(C-2) oligo- and poly-dihydropyridines derived from butanediol-l, 4-bis-3-aminocrotonate, or thiodiglycol bis-3-aminocrotonate and the end members 3-aminocrotonic acid methyl or ethyl ester, namely the Bis-dihydropyridines [121] and [122] (sulfur-free) as well as [123] and [124] (sulfur-containing). As well as the polydihydropyridines [125] and [126] (sulfur-free) as well as [127] and [128] (sulfur-containing). [127] and [128] are commercial products.

Preferred two or more combinations of at least one initial color improver (AFV) + at least one booster (A) are:

(BI): R ¹ or R ² = methyl, ethyl, propyl, butyl, cyclohexyl, AHyI, benzyl or hydrogen and (A).

(B-2): bisaminocrotonic acid ester of butanediol-1,4 or / and thiodiglycol and (A).

Named preferred combinations of two or more are:

1. two or more combinations of at least one compound (B-I) with at least one booster (A), namely:

(Bl) Component - Linear acyluricides: [1] with [Al] ₅ [A-2], [A-3], [A-4] and [A-5] wherein the combination with [Al] is very special is preferred. (Bl) Component - Cycloacylureides (6 (4) -iminobarbituric acids):

[21] with [A-I], [A-2], [A-3], [A-4] and [A-5] wherein the combination with [A-I] is most preferred.

(B-I) Component - Cyclo Acyl Acids (Aminouracils):

[41] with [A-I], [A-2], [A-3], [A-4] and [A-5]

[61] with [A-I], [A-2], [A-3], [A-4] and [A-5]

[66] with [A-I], [A-2], [A-3], [A-4] and [A-5]

[69] with [Al] ₅ [A-2], [A-3], [A-4] and [A-5] [81] with [Al], [A-2], [A-3] , [A-4] and [A-5]

[82] with [A-I], [A-2], [A-3], [A-4] and [A-5]

[95] with [A-I], [A-2], [A-3], [A-4] and [A-5]

[99] with [A-I], [A-2], [A-3], [A-4] and [A-5]

[103] with [A-I], [A-2], [A-3], [A-4] and [A-5] wherein the combination of [41] with [A-I] is most preferred.

(BI) Component - Cycloacylureides (hydantoins) [103a] with [Al], [A-2], [A-3], [A-4] and [A-5] [103b] with [Al] [A-2], [A-3], [A-4] and [A-5] wherein the combination of [103 a] with [Al] is most preferred.

2. Two or more combinations of at least one compound (B-2) with at least one booster (A), namely:

[116] with [Al], [A-2], [A-3], [A-4] and [A-5] [117] with [Al], [A-2], [A-3] , [A-4] and [A-5] wherein the combinations with [Al] are most preferred.

3. two or more combinations of at least one compound (C-I) with at least one booster (A), namely:

[118] with [Al], [A-2], [A-3], [A-4] and [A-5] [120] with [Al], [A-2], [A-3] , [A-4] and [A-5] wherein the combination of [120] with [Al] is most preferred.

4. two or more combinations of at least one compound (C-2) with at least one booster (A), namely: [127] with [Al], [A-2], [A-3], [A-4] and [A-5] [128] with [Al], [A-2], [A-3] , [A-4] and [A-5] wherein the combinations with [Al] are most preferred.

Of course, the compounds of classes (BI), (B-2), (CI) and (C-2) as well as the boosters [AI], [A-2], [A-3], [A-4 ] and [A-5].

The compounds from groups (A) and (B) are suitably used in the halogen-containing polymer from 0.01 to 10 phr, preferably from 0.05 to 5 and in particular from 0.1 to 3 phr, wherein (A) values in lower threshold range are preferred.

Furthermore, combinations with various HCl scavengers can be used, such as:

Alkali and alkaline earth compounds

This is understood to mean primarily the carboxylates of the acids described in the chapter zinc compounds, but also corresponding oxides or hydroxides or carbonates. They are also their mixtures with organic acids in question. Examples are LiOH, NaOH ₃ KOH, CaO, Ca (OH ₂ ), MgO, Mg (OH) ₂ , Sr (OH) ₂ , Al (OH) ₃ , CaCO ₃ and MgCO ₃ (also basic carbonates, such as magnesia, Alba and Huntit) _, as well as fatty Na and K salts. For alkaline earth and Zn carboxylates and their adducts with MO or M (OH) ₂ (M = Ca, Mg, Sr or Zn), so-called "overbased" compounds are used. In addition to the stabilizers according to the invention, preference is given to using alkali metal, alkaline earth metal and / or aluminum carboxylates.

Preference is given to magnesium hydroxide, Mg-acetylacetonate, Ca-acetylacetonate and uncoated and coated calcium hydroxide. Very particularly preferred is coated calcium hydroxide (coating with fatty acids, for example palmitic and stearic acids or mixtures thereof).

metal soaps

Metal soaps are mainly metal carboxylates, preferably longer chain carboxylic acids. Common examples are stearates and laurates, including oleates and salts of short-chain aliphatic or aromatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, sorbic acid; Oxalic acid, malonic acid, Succinic, glutaric, adipic, fumaric, citric, benzoic, salicylic, phthalic, hemimellitic, trimellitic, pyromellitic.

As metals may be mentioned: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce and rare earth metals. Often one uses so-called synergistic mixtures such as barium / zinc,

Magnesium / zinc, calcium / zinc or calcium / magnesium / zinc stabilizers. The

Metal soaps can be used individually or in mixtures. An overview of common metal soaps can be found in Ullmann's Encyclopedia of Industrial Chemistry,

5 ^th Ed., Vol. A16 (1985), p. 361 ff.). Preferred are magnesium, potassium and zinc soaps.

Preference is given to magnesium and calcium soaps. Very particular preference is given to magnesium and calcium laurate or stearate.

Zinc compounds: The zinc organic compounds having a Zn-OB are zinc ethers, zinc phenolates and / or zinc carboxylates. The latter are compounds from the series of the aliphatic saturated and unsaturated _Q-22 carboxylates, aliphatic saturated or unsaturated C _2-22 carboxylates which are substituted with at least one OH group or the chain interrupted by one or more O atoms, is (oxa acids), of the cyclic and bicyclic carboxylates having 5-22 C atoms, which is unsubstituted, substituted by at least one OH group and / or C _1-16 alkyl-substituted phenyl carboxylates, phenyl-the Cπ _ö alkylcarboxylates, or optionally with Crπ-alkyl-substituted phenolates, or abietic acid. Zn-S compounds are, for example, Zn-mercaptides, Zn-mercaptocarboxylates and Zn-mercaptocarboxylic acid esters.

Specifically, as examples, the zinc salts of monovalent carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid , Lauric, isostearic, stearic, 12-hydroxystearic, 9,10-dihydroxystearic, oleic, ricinoleic, 3,6-dioxaheptanoic, 3,6,9-trioxadecanoic, behenic, benzoic, p-tert-butylbenzoic,

Dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid. Cinnamic acid, mandelic acid, glycolic acid; Zinc salts of divalent carboxylic acids or their monoesters, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-l, 5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1, 7-dicarboxylic acid, octane-1, 8- dicarboxylic acid, 3,6,9-trioxadecane-1,10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, malic acid, salicylic acid, polyglycol dicarboxylic acid (n = 10-12), phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di- or tri-esters of tri- or tetravalent carboxylic acids, such as hemimellitic acid, trimellitic acid, pyromellitic acid, citric acid and also so-called overbased zinc carboxylates or ZinMaurylmerkaptid, zinc thioglycolate, zinc thiosalicylate, zinc bis-i-octyl thioglycolate, zinc mercaptopropionate, zinc thiolactate, zinc thiomalate , Zinc bis-octylmercaptopropionate, zinc bis-isooctylthiolactate and zinc bis-lauryl thiomalate.

The zinc olates are preferably enolates of acetylacetacetone, of benzoylacetacetone, of dibenzoylmethane and of enolates of acetoacetacetic and benzoylacetic esters and of dehydroacetic acid. In addition, inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate or zinc sulfide can be used.

Preference is given to neutral or basic zinc carboxylates of a carboxylic acid having 1 to 22 carbon atoms (zinc soaps), for example benzoates or alkanoates, preferably C ₈ -alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates and oleates, dihydroxystearates, p-tert-butylbenzoate, or (iso) octanoate. Particularly preferred are stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-ethylhexanoate.

The metal soaps or mixtures thereof can be used in an amount of, for example, 0.001 to 10 parts by weight, advantageously 0.01 to 8 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight PVC, are applied.

Hydrotalcites The chemical composition of these compounds is known to the person skilled in the art, for example from the publications PS - DE 38.43.581 A1, US Pat. No. 4,000,100, EP 0,062,813 A1 and WO 93/20135. These may be based on Al / Mg / carbonate, Al / Mg / Ti / carbonate, Li / Mg / carbonate or Li / Al / Mg / carbonate, as described in PS - DE 102.17.364 A1 (SüdChemie). , PS - DE 44.25266 Al (Metallgesellschaft), PS - EP 0.549.340 Al (Mizusawa Ind. Chem) and PS - JP 0.761.756 A1 (Fuji Chem. Ind.). Compounds of the hydrotalcite series by the following general formula: W

- 21 -

M ²⁺ _1-x M ₃ ⁺ _X (OH) ₂ (A ¹¹ U * d H ₂ O) wherein

M ²⁺ = as cation one or more of the metals from the group Mg ₃ Ca, Sr ₃ Zn or Sn, M ⁺ = as cation Al or B, A ^{n represents} an anion with the valence -n, b = n one Number of 1-2 is, O <x <0.5, d is a number from 0-20. Preference is given to compounds with

A ⁿ = OH ^" , ClO ₄ ^" , HCO ₃ ^" , CH ₃ COO ^" , C ₆ H ₅ COO ^" , CO ₃ ^2" , (CHOHCOO) ₂ ^{2 "} , (CH ₂ COO) ₂ ^{2 '} , CH ₃ CHOHCOO ^" , HPO ₃ ^" or HPO ₄ ^{2 "} .

Examples of hydrotalcites are

Al ₂ O ₃ * 6MgO * CO * 12H ₂ O, Mg _{4> 5} Al ₂ (OH) ₁₃ * CO ₃ * 3.5H ₂ O, 4MgO * Al ₂ O ₃ * CO ₂ * 9H ₂ O, 4MgO * Al ₂ O ₃ * CO ₂ * 6H ₂ O, ZnO * 3MgO * Al ₂ O ₃ * CO ₂ * 8-9 H ₂ O and

ZnO * 3MgO * Al ₂ O ₃ * CO ₂ * 5-6H ₂ O

Particularly preferred are the types Alkamizer 1 and 2, Alkamizer P 93-2 (manufacturer

Kyowa Chemical Ind. Co., JP) and L-CAM (Lithium Modified Hydrotalcite)

Lithium / carbonate / aluminum / magnesium, manufacturer Fuji Chem. Ind. Co. Ltd., JP: PS -

EP 0 761 756 A1 or Mizusawa Industrial Chemicals, Ltd., PS: EP 0549 340 A1 and Metallgesellschaft AG, PS - DE 4425266 C1). Very particular preference is given to using dehydrated hydrotalcites.

Titanium-containing hydrotalcites

Titanium-containing hydrotalcites are described in PS - WO 95/21127. Compounds of this type having the general formula Al _a Mgt, Ti _c (OH) d (CO ₃ ) _e * m H 2 O wherein a: b = 1: 1 to 1:10; 2 <b <10;

0 <c <5; O <m <5 and d and e are chosen so that a basic, charge-free molecule is formed, can also be used with.

Lithium layer lattice compounds (lithium hydrotalcites)

Lithium aluminum layer lattice compounds have the general formula:

Li _a M (b-2a) Al ( ₂ + a) OH ( _{4 + 2} b) (A ^{n '} ) ( _{2 /} n) _* m H ₂ O wherein

M is ^π Mg, Ca or Zn and A ^{n is} a selected anion of valency n or a mixture of anions and the indices are in the range of 0 <a <(b-2) / 2,

worinKb <6 and m = 0 to 30 are with the restriction that (b-2a)> 2 or the general formula:

wherein

M ^π , A, m and n have the above meaning and x satisfies 0.01 <x <1

The preparation of said Schicklite lattice compounds is characterized in that in the aqueous medium lithium hydroxide, oxide and / or its convertible into hydroxide compounds, metal (II) hydroxides, oxides and / or their hydroxides convertible compounds of said metals and aluminum hydroxides and / or their compounds convertible into hydroxides and acids and / or their salts or

Mixtures of which at a pH of 8 to 10 and at temperatures of 20 to 250 ⁰ C together and separates the resulting solid reaction product.

The reaction time is preferably 0.5 to 40 hours, especially 3 to 15 hours. The reaction product directly obtained from the reaction described above can be separated from the aqueous reaction medium by known methods, preferably by filtration. The workup of the separated reaction product is also carried out in a conventional manner, for example by washing the filter cake with water and drying the washed residue at temperatures of for example 60 to 150 ° C, preferably at 90 to 120 ° C.

For the reaction with aluminum, finely divided, active metal (III) hydroxide in combination with sodium hydroxide, as well as a NaAlO ₂ can be used. Lithium or one of the stated metal (II) compounds can be used in the form of finely divided lithium oxide or hydroxide or mixtures thereof or of finely divided metal (II) oxide or hydroxide or mixtures thereof. The corresponding acid anions can be used in differently concentrated form, for example directly as acid or else as salt.

The reaction temperatures are preferably between about 20 and 250 ° C, are more particularly between about 60 and 180 ⁰ C. Catalysts or accelerators not required. The substances can be removed as water of crystallization completely or partially by treatment. When used as stabilizers, the dried layer lattice compounds in customary for PVC processing temperatures of 160 to 22O ⁰ C columns from no water or another gas, so that no disturbing bubble formation occurs in the moldings.

The anion A "in the above general formula may include sulfate, sulfite, sulfide, thiosulfate, peroxosulfate, peroxodisulfate, hydrogenphosphate, hydrogenphosphite, carbonate, halides, nitrate, nitrite, hydrogensulfate, bicarbonate, hydrogensulfite, hydrogensulfide, dihydrogenphosphate, dihydrogenphosphite, monocarboxylic anions such as acetate and Benzoate, amide, azide, hydroxide, hydroxylamine, hydroazide, acetylacetonate, phenolate, pseudohalides, halogenites, halogenates, perhalates, I ₃ ^" , permanganate, dianions of dicarboxylic acids such as phthalate, oxalate, maleate or fumarate, bisphenolates, phosphate, pyrophosphate, phosphite, Pyrophosphite trianions of tricarboxylic acids such as citrate, trisphenolates and more, as well as mixtures thereof. Among them, hydroxide, carbonate, phosphite and maleate are preferable. To improve the dispersibility of the substances in halogen-containing thermoplastic polymer compositions, the same may be surface-treated with a higher fatty acid, eg stearic acid, an anionic surface-active agent, a silane coupler, a titanate coupler or a glycerin fatty acid ester.

Calcium aluminum hydroxo hydrogen phosphites

For the novel stabilizer combinations suitable compounds from the group of basic calcium-aluminum-hydroxy-hydrogen phosphites of the general formula

Ca _x Al ₂ (OH) _{2 (x + 2)} HPO _{3 *} H ₂ O, where x = 2 - 8 and

Ca _x Al ₂ (OH) _{2 (x + 3-y)} (HPO ₃ ) y _* mH ₂ 0, where x = 2 - 12, 2x + 5>v> 0

2 and m = 0 - 12, except y = 1, when x = 2 - 8,

can be prepared for example by a method in which mixtures of calcium hydroxide and / or calcium oxide, aluminum hydroxide and

Sodium oxide or from calcium hydroxide and / or calcium oxide and sodium aluminate with converts phosphorous acid in amounts corresponding to the production of the desired calcium aluminum hydroxyhydrogen phosphites in aqueous medium and the reaction product in a conventional manner separated and recovered. The reaction product directly obtained from the reaction described above can be separated from the aqueous reaction medium by known methods, preferably, for example by washing the filter cake with water and drying the washed residue at temperatures of for example 60-13O ⁰ C, preferably 90-120 ⁰ C.

For the implementation, both finely divided, active aluminum hydroxide in combination with sodium hydroxide and a sodium aluminate Weden used. Calcium may be used in the form of finely divided calcium oxide or calcium hydroxide or mixtures thereof. The phosphorous acid can be used in different concentrated form. The reaction temperatures are preferably between 50 and 100 ° C, more preferably between about 60 and 85 ° C. Catalysts or accelerators are not required, but do not interfere with the compounds, the water of crystallization can be wholly or partially removed by thermal treatment.

When used as stabilizers, the dried calcium-aluminum-hydroxy-phosphites do not split off water at the processing temperatures of 160-200 ° C., which are customary, for example, for rigid PVC, so that no disturbing bubble formation occurs in the molded parts.

To improve their dispersibility in halogen-containing thermoplastic resins, the compounds can be coated in a known manner with surfactants. The class of compounds, also called CHAP or CAP compounds, is described in EP 0.506.83 IAl

The above-described calcium-aluminum hydroxo-hydrogen phosphites and titanium-containing hydrotalcites may be crystalline and also partially crystalline and / or amorphous.

Zeolites (alkali or alkaline earth metal aluminosilicates)

They can be described by the formula Mχ _{/ n} [(AlO ₂ ) _x (SiO ₂ ) _y ] _* w H ₂ O, where n is the charge of the cation M; M is an element of the first or second main group, such as Li, Na ₅ K or NH ₄ and Mg, Ca, Sr or Ba; y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.

Examples of zeolites are sodium aluminosilicates of the formulas Na ₁₂ Al ₁₂ Si ₁₂ O _{48 *} 27 H ₂ O [zeolite A], Na ₆ Al ₆ Si ₆ O ₂₄ ^ NaX _* 7.5 H ₂ O, X = OH, halogen, ClO ₄ [sodalite]; Na ₆ Al ₆ Si ₃₀ O _{72 *} 24 H ₂ O; Na ₈ Al ₈ Si ₄₀ O _{96 *} 24 H ₂ O;

Na ₁₆ Ali ₆ Si ₂₄ O _{80 *} 16 H ₂ O; Na ₁₆ Al ₁₆ Si ₃₂ O _{96 *} 16 H ₂ O; Na ₅₆ Al ₅₆ Si ₁₃₆ O _{384 *} 250 H ₂ O [zeolite Y], Na ₈₆ Al ₈₆ Si ₁₀₆ O _{384 *} 264 H ₂ O [zeolite X]; Na ₂ O, Al ₂ O _3, (2-5) SiO _2, (3,5-1O) H ₂ O [zeolite P]; Na ₂ O, Al ₂ O ₃ , 2SiO ₂ , _* (3,5-10) H ₂ O (zeolite MAP); or the zeolites which can be prepared by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as (Na ₃ K) ₁₀ Al ₁₀ Si ₂₂ O _{64 *} 20 H ₂ O; Ca _4j5 Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] _* 30 H ₂ O; K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] _* 27 H ₂ O. Very particular preference is given to Na zeolite A and Na zeolite MAP (see also PS - US Pat. No. 6,531,533). Also preferred are zeolites with extremely small particle size, in particular of the Na-A and Na-P type, as described in PS - US 6,096,820.

Dawsonite (Alkalialumocarbonate)

These are given by the general formula

M [Al (OH) ₂ CO ₃ ] (M = Na, K). The preparation of Na-Dawsonite (DASC or SAC) and K-Dawsonite (DAPC) is published in PS-US 3.501.264 and US 4.221.771 as well as in PS-EP 0394.670 A1. The synthesis can be carried out hydrothermally or non-hydrothermally. The products may be crystalline or amorphous. Also included in the substance class are sodium magnesium alumino carbonates (SMAC); their preparation is described PS - US 455.055.284.

The hydrotalcites and / or calcium-aluminum hydroxo-hydrogen phosphites and / or zeolites and / or dawsonites can be obtained in quantities of, for example, from 0.1 to 20, advantageously from 0.1 to 10 and in particular from 0.1 to 5, parts by weight to 100 parts by weight of halogen-containing polymer.

glycidyl

They contain the glycidyl group,

wherein this is bonded directly to carbon, oxygen, nitrogen or sulfur atoms, and wherein either R ₃ and R _{5 are} both hydrogen, R _{4 is} hydrogen or methyl and n = 0, or wherein R ₃ and R ₅ together are -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -, then R ₄ is hydrogen and n = 0 or 1.

I) glycidyl and .beta.-methylglycidyl esters obtainable by reacting a compound having at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or .beta.-methyl-epichlorohydrin. The reaction is conveniently carried out in the presence of bases.

As compounds having at least one carboxyl group in the molecule, aliphatic carboxylic acids can be used. Examples of these carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic and methacrylic acid, caproic, caprylic, lauric, myristic, palmitic, stearic and pelargonic acids, as well as in the organic zinc compounds mentioned acids.

However, it is also possible to use cycloaliphatic carboxylic acids, for example cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

It is also possible to use aromatic carboxylic acids, for example benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

Also, carboxyl-terminated adducts, for. Trimellitic acid and polyols such as glycerol or 2,2-bis- (4-hydroxycyclohexyl) -propane. Further epoxide compounds which can be used in the context of this invention can be found in EP 0 506 617. II) glycidyl or (.beta.-methylglycidyl) ethers obtainable by reacting a compound having at least one free alcoholic hydroxyl group and / or phenolic hydroxyl group and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.

Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-l, 2-diol, or poly (oxypropylene) glycols, propane-l, 3 diol, butane-1,4-diol, poly (oxytetramethylene) -glycols, pentane-l, 5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1, 1-trimethylol propane, bistrimethylolpropane, pentaerythritol, sorbitol, as well as polyepichlorohydrins, butanol, amyl alcohol, pentanol, and monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol and C ₇ -C ₉ - alkanol and C ₉ -C _{1 j} -Alkanolgemischen.

However, they are also derived, for example, from cycloaliphatic alcohols, such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) -propane or 1, L-bis (hydroxymethyl) cyclohex-3-ene or they have aromatic nuclei such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.

The epoxy compounds may also be derived from mononuclear phenols, such as phenol, resorcinol or hydroquinone; or they are based on polynuclear phenols, for example on bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-) hydroxyphenyl) propane, 4,4'-dihydroxydiphenylsulfone or condensation products of phenols with formaldehyde such as phenol novolacs obtained under acidic conditions.

Further possible terminal epoxides are, for example: glycidyl 1-naphthyl ether, grycidyl 2-phenylphenyl ether, 2-biphenylglycidyl ether, N- (2,3-epoxypropyl) phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether.

III) (N-glycidyl) compounds obtainable by dehydrochlorinating the reaction products of epichlorohydrin with amines containing at least one amino hydrogen atom. These amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis (4-aminophenyl) methane, m-xylylenediamine or bis (4-aminophenyl) methane. methylaminophenyl) methane, but also N, N, O-triglycidyl-m-aminophenol or N ₅ N ₅ O-triglycidyl-p-aminophenol.

The (N-glycidyl) compounds also include N, N'-di-, N, N ', N "-Tri- and N, N', N", N "'- Tetraglycidylderivate of cycloalkylene, such as ethyleneurea or 1,3-propyleneurea, and N, N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

IV) S-glycidyl compounds such as di-S-glycidyl derivatives derived from dithiols such as ethane-l, 2-dithiol or bis (4-mercaptomethylphenyl) ether.

V) Epoxide compounds having a radical of the above formula in which R 1 and R 3 together are --CH 2 --CH 2 - and n is 0 are bis (2,3-epoxycyclopentyl) ethers, 2,3-epoxycyclopentylglycidyl ethers or 1,2 bis (2,3-epoxycyclopentyloxy) ethane. An epoxy resin having a radical of the above formula in which Ri and R3 together are -CH 2 -CH 2 - and n is 1 is, for example, 3,4-epoxy-6-methylcyclohexanecarboxylic acid (3 ', 4'-epoxy-6' methyl cyclohexyl) methyl ester.

Examples of suitable terminal epoxides are: a) liquid bisphenol A diglycidyl ethers such as Araldit®GY 240, Araldit®GY 250, Araldit®GY 260, Araldit® GY 266, Araldit® GY 2600, Araldit®MY 790 and Epicote® 828 (BADGE ); b) solid bisphenol A diglycidyl ethers such as Araldit® GT 6071, Araldit® GT 7071, Araldit® GT 7072, Araldit® GT 6063, Araldit® GT 7203, Araldit® GT 6064, Araldit® GT

7304, Araldit® GT 7004, Araldit® GT 6084, Araldit® GT 1999, Araldit® GT 7077, Araldit® GT 6097, Araldit® GS 7097, Araldit® GS 7008, Araldite® GT 6099, Araldite® GS 6608, Araldite® GS 6609, Araldit® GT 6610 and Epikote® 1002; c) liquid bisphenol F diglycidyl ethers such as Araldit®GY 281, Araldit®PY 302, Araldit®PY 306 (BFDGE);

D) solid polyglycidyl ethers of tetraphenylethane such as CG Epoxy Resin 0163; e) solid and liquid polyglycidyl ethers of phenolformaldehyde novolaks such as EPN 1138, EPN 1139, GY 1180, PY 307 (NODGE); f) solid and liquid polyglycidyl ethers of o-cresol formaldehyde novolac such as ECN 1235, ECN 1273, ECN 1280, ECN 1299 (NODGE); g) liquid glycidyl ethers of alcohols such as Shell Glycidyl ether® 162, Araldit® DY 0390, Araldit® DY 0391; h) liquid and solid glycidyl esters of carboxylic acids such as Shell Cardura E terephthalic acid esters, trimellitic acid esters and mixtures thereof Araldit® PY 284 and Araldit® P811; i) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit® PT 810; j) liquid cycloaliphatic epoxy resins such as Araldit® CY 179; k) liquid N, N, O-triglycidyl ethers of p-aminophenol such as Araldit® MY 0510;

1) Tetraglycidyl-4-4'-methylenebenzamine or N, N, N ', N'-tetraglycidyldiaminophenylmethane such as Araldit®MY 720, Araldit®MY 721.

Epoxy compounds having two functional groups are preferably used. However, it is also possible in principle to use epoxide compounds having one, three or more functional groups.

Primarily epoxy compounds, especially diglycidyl compounds, are used with aromatic groups.

Optionally, a mixture of different epoxy compounds can be used.

Particularly preferred terminal epoxide compounds are diglycidyl ethers based on bisphenols, such as, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane or mixtures of bis ( ortho / para-hydroxyphenyl) -methane (bisphenol-F).

The terminal epoxide compounds can be used in an amount of preferably at least 0.1 part, for example 0.1 to 50, advantageously 1 to 30 and in particular 1 to 25 parts by weight, based on 100 parts by weight of PVC.

Very particular preference is given to bisglycidyl alcohol ethers of the formula (D)

(D) wobei

(D) where

R ³ = unbranched or branched C ₂ -C ₂₀ -alkylene, which may be interrupted by 1 to 4 O or S atoms and / or substituted by 1 to 4 OH groups, or dimethylol-cyclohexane-l, 4-diyl , Polyethylene (or -propylene) glycol-oc, ω-diyl (preferably, poly = tetra to deca), polyglyceryl-α, ω-diyl (preferably, poly-tetra to deca) or glycerol-triyl, trimethylolethane (or -propane) ) triyl, pentaerythritol tri (or tetra) yl, bis-trimethylolethane (or propane) tri (or tetra) yl, diglycerol tri (or tetra) yl, tetrit tetrayl, triglycerol tri (or -tetra, -penta) yl,

Pentitol pentyl, dipentaerythritol penta (or hexa) yl and hexitol hexyl; and m = 2, 3, 4, 5 or 6

Also suitable are bisglycidyl alcohol ethers of alkanediols, diglycols, tri- and tetraglycols (glycol = ethylene or propylene glycol) and polyglycols, and of [118a] glycerol and polyglycerols as well as 1,4-cyclohexanedimethanol [118b]. Tris-epoxypropyl alcohol ethers of [119a] glycerol and [120a, 121a] trimethylolethane (propane); and [121b, 121c] triethylol (-isopropylol) isocyanurate (THEIC) and tetrakis-epoxypropyl alcohol ethers of [122a, 123a] bis-trimethylolethane (propane ) and hexakis-epoxypropyl alcohol ethers of [124a] dipentaerythritol and [125a] sorbitol. Particularly noteworthy are [126a] hexanediol and [127a] neopentyl glycol diglycidyl ethers and [128a] ethylene glycol diglycidyl ether, [129] diethylene glycol and [130] dipropyleneglycol and polyglycerol, [131] diglycerol, [132] triglycerol. , [133] tetraglycerol and [134] pentaglycerol diglycidyl ether, [135] butanediol-1,4-diglycidyl ether, [136, 137] trimethylolethane (propane) diglycidyl ether, and [138, 139] pentaerythritol tri- and tetraglycidyl ethers and polyglycerol -triglycidylether. Preference is given to [118a], [118b], [119a], [120a], [121a], [126a], [127a], [128a], [129], [130], [131], [132] [133], [134], [135], [136], [137], [138], and [139]. Particularly preferred are [118a], [118b], [119a], [120a], [121a], [126a], [127a], [128a], [129], [130], [135], [136] , [137], [138] and [139]. Most preferred are [118a], [118b], [119a], [120a], [121a], [126a], [135], [136], [137], [138] and [139]. Many compounds of this series are produced as "bulk" chemicals.

Epoxidized fatty acid esters and other epoxide compounds The novel stabilizer combination may additionally preferably contain at least one epoxidized fatty acid ester. It comes mainly for esters of Fatty acids from natural sources (fatty acid glycerides), such as soybean oil or rapeseed oil, in question. But it can also be synthetic products such as epoxidized butyl oleate used. It is likewise possible to use epoxidized polybutadiene and polyisoprene, if appropriate also in partially hydroxylated form, or glycidyl acrylate and glycidyl methacrylate as homo- or copolymer. These epoxy compounds may also be applied to an alumino salt compound; see also DE 4.031.818 A1.

Liquid or highly viscous glycidyl or epoxy compounds can also be applied to siliceous or silicate-containing carriers and used in a solid, non-sticky form.

phenolic compounds

This category includes phenols and aminophenols such as resorcinol, resorcinol monomethyl ether, phloroglucinol, 2-naphthol, 3-hydroxyaniline and 3-hydroxydiphenylamine.

Preferably contain stabilizer systems according to the invention

Cyanamide compounds of the formula (E)

(E)

in which

R ⁴ independently of one another = H, nitrile, carbamoyl, R ¹ , R ² , R ¹ CO, R ² CO, Na ₃ K,

Mg _{ϊ / 2} and Ca ₁ ^ or R ₂ ⁴ = tetra-, penta- or hexamethylene and o = 1, 2 or 3.

(E) Monomeric cyanamides: [140] cyanamide and its salts, in particular [141] calcium cyanamide, [142] monomethyl, [143] monoethyl, [144] monopropyl, [145] monobutyl, [146] monopentyl, [147] Monohexyl, [148] monoheptyl, [149] monooctyl, [150] monophenyl, and [151] monobenzyl cyanamide, and [152] monoallyl cyanamide. [153] 1,1-dimethyl, [154] 1,1-diethyl, [155] 1,1-dipropyl, [156] 1,1-dibutyl, [157] 1,1-dipentyl, [158] 1,1-dihexyl, [159] l, l, diheptyl, [160] 1,1-dioctyl, [161] 1,1-diphenyl, and [162] 1,1-dibenzyl cyanamide, and [163 ] 1,1-diallylcyanamide.

[164] acetyl, [165] propionyl, [166] butyroyl, [167] pentanoyl, [168] hexanoyl, [169] heptanoyl, [170] octanoyl, [171] nonanoyl, [172] Decanoyl, [173] undecanoyl, [174] dodecanoyl, [175] tridecanoyl, [176] tetradecanoyl, [177] pentadecanoyl, [178] hexadecanoyl, [179] heptadecanoyl, [180] octadecanoyl, , [181] nonadecanoyl, [182] eicosanoylcyanamide, [183] benzoylcyanamide, and [184] tetradecyl, [185] hexadecyl, and [186] octadecylcyanamide. Since cyanamide (derivative) is u.U.U. in the PVC processing. prone to decomposition, it is advisable in reactive representatives vorabompounding in a hot mixer.

(E) dimers: [187] dicyandiamide and its substitution products and their salts. Preferably, the unsubstituted dicyandiamide.

(E) trimers: melamine (s) e, such as [188] melamine, [189] melamine perchlorate, [190] oxalate, [191] sulfate, [192] nitrate, [193] - {pyro, poly) phosphate , borate and [194] - isocyanurate. Preferred are [188], [189], [193] and [194].

N-substituted melamines such as [195] N-monobutyl, [196] N-monooctyl, [197] N-monodecyl, [198] N-monododecyl, [199] N-monotetradecyl, [200] N Monohexadecyl, [201] N-monooctadecyl, [202] N-monophenylmelamine. And [203] N-monoacetyl, [204] N-monopropionyl, [205] N-monobutyroylmelamine, [206] N-monophenyl, [207] N-monoallyl, and [208] N-monobenzylmelamine, [209] o Hydroxyphenylmelamine and [210,211] 2-hydroxyethyl (propyl) -melamine.

N ₅ N'-substituted melamines such as [212] N, N'-dibutyl, [213] N, N'-dioctyl, [214] N ₃ N'-didecyl, [215] N, N'- Dihexadecyl- and [216] N, N'-dioctadecylmelamine and [217,218] N, N'-bis-2-hydroxyethyl (propyl) melamine.

N, N ', N "-substituted melamines, such as [219] N, N', N" -tributyl, [220] N, N ', N "-trioctyl-, [221] N, N', N" Tridecyl, [222] N, N ' ₅ N "-tetradecyl, [223] N ₃ N', N" -trihexadecyl and [224] N, N ', N "-trioctadecylmelamine, and [225] N, N ', N'-phenyl-bis-hydroxyethyl and [226] N, N', N "-tris-hydroxyethylmelamine, [227] N ₅ N ', N" -triacetyl- ₅ [228] N, N', N "Tripropionyl, [229] N, N ' ₅ N" -Tribenzoylmelamine and [230] N, N', N "-Triallyl- and [231] N, N ', N "-Tribenzylmelamine, [232] N, N', N" -triphenylmelamine, and [233] N ₅ N ₅ N "-tricyclohexylmelamine, [234] N, N ', N" -Tris -hydroxypropylmelamine and [235] N ₅ N ' ₅ N "-phenyl-bis-hydroxypropylmelamine.

The substances [141], [142], [143], [144], [150], [151], [153], [154], [155], [159], [162], [163 ], [164], [176], [178], [184], [185] and [186], [187] and [188]. Furthermore, preference is given to [206], [207], [208], [209], [210], [211]. Also preferred are [217,218], [226], [227], [228], [229], [230] and [231].

Particularly preferred are [187], [188], [209], [210] and [211]. Furthermore, particular preference is given to [226] [227] [228] [229] [230] and [231]. Very particularly preferred are [141], [187], [188] and [194] in micronized form (particle size <50 μm).

Likewise, very particular preference is given. the calcium and magnesium salts of [187], [188], or [194] are so-called "commodities." The Ca and Mg salts can also be synthesized "in situ" during PVC processing, or previously in the Formulation or compounding of magnesium or calcium hydroxide are produced

The melting-point decomposition of [187] is eutectic with N, N'-disubstituted

(Thio) ureas or aniline derivatives or with aminobenzenesulfonamides particularly preferred.

5. Preferred two or more combinations of at least one HCl scavenger (SCV) + at least one booster (A) are ^* :

[232] CaH (u) ⁵⁾ with [Al] ₅ [A-2], [A-3] ₅ [A-4] and [A-5]

[233] CaH (c) ⁶⁾ with [Al] ₅ [A-2], [A-3], [A-4], and [A-5]

[234] MgH ^π) with [Al], [A-2] ₅ [A-3], [A-4], and [A-5]

[235] CaAcac ¹²⁾ with [Al] ₅ [A-2], [A-3] ₅ [A-4], and [A-5]

[236] MgAcac ¹³⁾ with [Al] ₅ [A-2] ₅ [A-3] ₅ [A-4] and [A-5] [237] CaSt ³⁸⁾ with [Al] ₅ [A-2] , [A-3] ₅ [A-4] and [A-5]

[238] MgSt ³⁷ Wt [Al], [A-2], [A-3], [A-4] and [A-5]

[239] Hytal ⁷⁾ with [Al] ₅ [A-2] ₅ [A-3], [A-4] and [A-5]

[240] NaZA ¹⁰⁾ with [Al] ₅ [A-2], [A-3], [A-4], and [A-5]

[241] HEXDGE ²⁹⁾ with [AI] ₅ [A-2], [A-3], [A-4] and [A-5] [241a] c-HEXDGE ^29a) with [AI], [A- 2], [A-3], [A-4] and [A-5]

^{* For} footnotes and abbreviations see Patent Applications Application Technology [242] BADGE ²⁵⁾ with [AI], [A-2], [A-3], [A-4] and [A-5] [243] BFDGE ²⁶⁾ with [AI], [A-2] , [A-3], [A-4] and [A-5] [244] Glydi ³⁰⁾ with [Al], [A-2], [A-3], [A-4] and [A-] 5] [245] Glytri ³¹⁾ with [Al] ₃ [A-2], [A-3], [A-4] and [A-5] [246] ESBO ⁵⁷⁾ with [Al] ₃ [A- 2], [A-3], [A-4] and [A-5] [247] DCN ²⁰⁾ with [Al], [A-2], [A-3], [A-4] and [ A-5] [248] Mel ²³⁾ with [AI], [A-2], [A-3], [A-4] and [A-5] [249] ACEGA ²⁴⁾ with [AI], [ A-2], [A-3], [A-4] and [A-5] [250] TEPC ³²⁾ with [Al], [A-2], [A-3], [A-4] and [A-5] [251] Cardura ³⁵⁾ with [AI], [A-2], [A-3], [A-4] and [A-5] wherein the combinations in [232], [233 ], [241], [241a] and [248] each with [AI] are most preferred.

6. Also preferred are triple or multiple combinations of at least two different scavengers (SCV) and at least one booster (A):

[232a] CaH (u) ⁵⁾ with Mel ²³⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [233] CaH (c) ⁶⁾ with Mel ²³⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [233b] CaH (c) ⁶⁾ with CaSt ³⁸⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] wherein the combination in [232a] with [Al] is most preferred.

7. Particularly preferred are triple or multiple combinations of at least one initial color improver (AFV) from the compound classes (BI), (B-2), (CI), (C-2) with at least one scavenger (SCV) and at least one booster ( A):

[252] CADMU ⁴⁴⁾ with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [253] CADMU ⁴⁴⁾ with CaH (FIG. c) ⁶⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [254] CADMU ⁴⁴⁾ with MgH ^11} and [Al], [A- 2], [A-3], [A-4] and [A-5] [255] CADMU ⁴⁴⁾ with CaAcac ¹²⁾ and [AI], [A-2], [A-3], [A- 4] and [A-5] [256] CADMU ⁴⁴⁾ with MgAcac ¹³⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [257] CADMU ⁴⁴⁾ with CaSt ³⁸⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [258] CADMU ⁴⁴⁾ with MgSt ³⁷⁾ and [Al], [ A-2], [A-3], [A-4] and [A-5] [259] CADMU ⁴⁴⁾ with Hytal ⁷⁾ and [Al], [A-2], [A-3], [ A-4] and [A-5] [260] CADMU ⁴⁴⁾ with NaZA ¹⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [261 CADMU ⁴⁴⁾ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [261a] CADMU ⁴⁴ Wt c-HEXDGE ^29a) and [AI ], [A-2], [A-3], [A-4], and [A-5] [262] CÄDMU ⁴⁴⁾ with BADGE ²⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [263] CADMU ⁴⁴⁾ with BFDGE ²⁶⁾ and [ Al], [A-2], [A-3], [A-4] and [A-5] [264] CADMU ⁴⁴⁾ with Glydi ³⁰⁾ and [Al], [A-2], [A- 3], [A-4] and [A-5] [265] CADMU ⁴⁴⁾ with Glytri ³¹⁾ and [AI] ₅ [A-2], [A-3], [A-4] and [A-4]. 5] [266] CADMU ⁴⁴⁾ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [267] CADMU ⁴⁴⁾ with DCN ²⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [268] CADMU ⁴⁴⁾ with Mel ²³⁾ and [Al], [A-2], [ A-3], [A-4] and [A-5] [269] CADMU ⁴⁴⁾ with ACEGA ²⁴⁾ and [AI], [A-2], [A-3], [A-4] and [ A-5] [270] CADMU ⁴⁴⁾ with TEPC ³²⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [271] CADMU ⁴⁴⁾ with Cardura ³⁵⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] wherein [252], [253], [261], [261a], and [268] are very particularly preferred. Highlighted here are the combinations with [AI].

[272] DMAU ⁴³⁾ with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [273] DMAU ⁴³⁾ with CaH (cf. c) ⁶⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [274] DMAU ⁴³⁾ with MgH ⁿ⁾ and [Al], [A-] 2], [A-3], [A-4] and [A-5] [275] DMAU ⁴³⁾ with CaAcac ¹²⁾ and [AI], [A-2], [A-3], [A- 4] as well as [A-5] [276] DMAU ⁴³⁾ with MgAcac ¹³⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [277] DMAU ⁴³⁾ with CaSt ³⁸⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [278] DMAU ⁴³⁾ with MgSt ³⁷ Wd [Al], [A -2], [A-3], [A-4] and [A-5] [279] DMAU ⁴³⁾ with Hytal ⁷⁾ and [Al], [A-2], [A-3], [A -4] and [A-5] [280] DMAU ^{43) with} NaZA ¹⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [281] DMAU ⁴³⁾ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [281a] DMAU ⁴³⁾ with c-HEXDGE ^29a) and [AI] , [A-2], [A-3], [A-4], and [A-5] [282] DMAU ⁴³⁾ having BADGE ²⁵⁾ and [AI], [A-2], [A-3] , [A-4] and [A-5] [283] DMAU ⁴³⁾ with BFDGE ²⁶⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [284] DMAU ⁴³⁾ with Glydi ³⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [285] DM AU ⁴³⁾ with Glytri ³¹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [286] DMAU ⁴³⁾ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [287] DMAU ⁴³⁾ with DCN ²⁰⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [288] DMAU ⁴³⁾ with Mel ²³⁾ and [Al], [A-2], [A-3], [A-4], and [A-5] 289] DMAU ⁴³⁾ with ACEGA ²⁴⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [290] DMAU ⁴³⁾ with TEPC ³²⁾ and [AI ], [A-2], [A-3], [A-4], and [A-5] [291] DMAU ⁴³⁾ with Cardura ³⁵⁾ and [AI], [A-2], [A-3 ], [A-4] and [A-5] wherein [272], [273], [281], [281a] and [288] are most preferred. Highlighted here are the combinations with [AI]. [292] AC-1 ⁴¹⁾ with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [293] AC-1 ^{41 )} with CaH (c) ⁶⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [294] AC-1 ⁴¹⁾ with MgH ^u) and [ Al], [A-2], [A-3], [A-4] and [A-5] [295] AC-1 ⁴¹⁾ with CaAcac ¹²⁾ and [Al], [A-2], [ A-3], [A-4], and [A-5] [296] AC-1 ⁴¹⁾ with MgAcac ¹³⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [297] AC-1 ⁴¹⁾ with CaSt ³⁸⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [298] AC -1 ⁴¹⁾ with MgSt ³⁷ W [Al], [A-2], [A-3], [A-4] and [A-5] [299] AC- ⁴¹⁾ with Hytal ⁷⁾ and [AI ], [A-2], [A-3], [A-4], and [A-5] [300] AC-1 ⁴¹⁾ with NaZA ¹⁰⁾ and [AI], [A-2], [A -3], [A-4] and [A-5]

[301] AC-1 ⁴¹⁾ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [301a] AC-1 ⁴¹⁾ with c -HEXDGE ^29a) and [AI], [A-2], [A-3], [A-4] and [A-5] [302] AC-1 ⁴¹⁾ with BADGE ²⁵⁾ and [AI], [ A-2], [A-3], [A-4], and [A-5] [303] AC-1 ⁴¹⁾ with BFDGE ²⁶⁾ and [AI], [A-2], [A-3] , [A-4] and [A-5] [304] AC-1 ⁴¹⁾ with Glydi ³⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A- 5] [305] AC-1 ⁴¹⁾ with Glytri ³¹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [306] AC-1 ⁴¹⁾ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [307] AC-1 ⁴¹⁾ with DCN ²⁰⁾ and [AI], [ A-2], [A-3], [A-4], and [A-5] [308] AC-1 ⁴¹⁾ with Mel ²³⁾ and [Al], [A-2], [A-3] , [A-4] and [A-5] [309] AC-1 ⁴¹⁾ with ACEGA ²⁴⁾ and [AI], [A-2], [A-3], [A-4] and [A- 5] [310] AC-1 ⁴¹⁾ with TEPC ³²⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [311] AC-1 ⁴¹⁾ with Cardura ³⁵⁾ and [Al], [A-2], [A-3], [A-4], and [A-5] wherein [292], [293], [301], [301a], and [ 308] are very particularly preferred. Highlighted here are the combinations with [AI].

[312] AC-2 ⁴²⁾ with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [313] AC-2 ^{42 )} with CaH (c) ⁶⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [314] AC-2 ⁴²⁾ with MgH ^π) and [ Al], [A-2], [A-3], [A-4] and [A-5] [315] AC-2 ⁴²⁾ with CaAcac ¹²⁾ and [Al], [A-2], [ A-3], [A-4] and [A-5] [316] AC-2 ⁴² with MgAcac ¹³⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [317] AC-2 ⁴²⁾ with CaSt ³⁸⁾ and [Al], [A-2], [A-3], [A-4], and [A-5] [318] AC -2 ⁴²⁾ with MgSt ³⁷ W [Al], [A-2], [A-3], [A-4] and [A-5] [319] AC-2 ⁴²⁾ with Hytal ⁷⁾ and [Al ], [A-2], [A-3], [A-4], and [A-5] [320] AC-2 ⁴²⁾ with NaZA ¹⁰⁾ and [AI], [A-2], [A -3], [A-4] and [A-5] [321] AC-2 ⁴²⁾ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [321a] AC-2 ⁴²⁾ with c-HEXDGE ^29a) and [AI], [A-2], [A-3], [A-4], and [A-5] [322] AC-2 ⁴²⁾ with BADGE ²⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [323] AC-2 ⁴²⁾ with BFDGE ²⁶⁾ and [AI] ₃ [A-2], [A-3], [A-4] and [A-5] [324] AC-2 ⁴²⁾ with Glydi ³⁰⁾ and [AI], [A- 2], [A-3], [A-4] and [A-5] [325] AC-2 ⁴²⁾ with Glytri ³¹⁾ and [AI], [A-2], [A-3], [ A-4] and [A-5] [326] AC-2 ⁴²⁾ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [327] AC-2 ⁴²⁾ with DCN ²⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [328] AC-2 ⁴²⁾ with Mel ²³⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [329] AC-2 ⁴²⁾ with ACEGA ²⁴⁾ and [AI], [A- 2], [A-3], [A-4] and [A-5] [330] AC-2 ⁴²⁾ with TEPC ³²⁾ and [AI], [A-2], [A-3], [ A-4] and [A-5] [331] AC-2 ⁴²⁾ with Caxdura ³⁵⁾ and [Al], [A-2], [A-3], [A-4], and [A-5] wherein [312], [313], [321], [321a] and [328] are most preferred. Highlighted here are the combinations with [AI].

[332] M-DHP-1 with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [333] M-DHP-1 ⁴⁶⁾ with CaH (c) ⁶⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [334] M-DHP-1 ⁴⁶⁾ with MgH ^{n )} and [AI], [A-2], [A-3], [A-4] and [A-5] [335] M-DHP-1 ⁴⁶⁾ with CaAcac ¹²⁾ and [AI], [A -2], [A-3], [A-4] and [A-5] [336] M-DHP-1 ⁴⁶⁾ with MgAcac ¹³⁾ and [AI], [A-2], [A-3 ], [A-4] and [A-5] [337] M-DHP-1 ⁴⁶⁾ with CaSt ³⁸⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [338] M-DHP-1 ⁴⁶⁾ with MgSt ³⁷ Wd [Al], [A-2], [A-3], [A-4], and [A-5] [339] M -DHP-I ⁴⁶⁾ with Hytal ⁷⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [340] M-DHP-1 ^{46) with} NaZA ^{10 )} and [AI], [A-2], [A-3], [A-4] and [A-5] [341] M-DHP-1 ⁴⁶⁾ with HEXDGE ²⁹⁾ and [AI], [A -2], [A-3], [A-4] and [A-5] [341a] M-DHP-1 ⁴⁶⁾ with c-HEXDGE ^29a) and [AI], [A-2], [A -3], [A-4] and [A-5] [342] M-DHP-1 ⁴⁶⁾ with BADGE ²⁵⁾ and [AI], [A-2], [A-3], [A-4 ] and [A-5] [343] M-DHP-1 ⁴⁶⁾ with BFDGE ²⁶⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [ 344] M-DHP-1 ⁴⁶⁾ with Glydi ³⁰⁾ and [AI], [A- 2], [A-3], [A-4] and [A-5] [345] M-DHP-1 ⁴⁶⁾ with Glytri ³¹⁾ and [Al], [A-2], [A-3] , [A-4] and [A-5] [346] M-DHP-1 ⁴⁶⁾ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4] and [ A-5] [347] M-DHP-1 ⁴⁶⁾ with DCN ²⁰⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [348] M -DHP-1 ⁴⁶⁾ with Mel ²³⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [349] M-DHP-I ⁴⁶⁾ with ACEGA ²⁴⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [350] M-DHP-1 ⁴⁶⁾ with TEPC ³²⁾ and [AI], [ A-2], [A-3], [A-4] and [A-5] [351] M-DHP-1 ⁴⁶⁾ with Cardura ³⁵⁾ and [AI], [A-2], [A- 3], [A-4] and [A-5] wherein [332], [333], [341], [341a] and [348] are most preferred. Highlighted here are the combinations with [AI]. [352] M-DHP-2 ⁴⁷⁾ with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [353] M DHP-2 ⁴⁷⁾ with CaH (c) ⁶⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [354] M-DHP-2 ⁴⁷⁾ with MgH ^U) and [AI], [A-2], [A-3], [A-4] and [A-5] [355] M-DHP-2 ⁴⁷⁾ with CaAcac ¹²⁾ and [AI] , [A-2], [A-3], [A-4] and [A-5] [356] M-DHP-2 ⁴⁷⁾ with MgAcac ¹³⁾ and [Al], [A-2], [ A-3], [A-4] and [A-5] [357] M-DHP-2 ⁴⁷⁾ with CaSt ³⁸⁾ and [AI], [A-2], [A-3], [A- 4] and [A-5] [358] M-DHP-2 ⁴⁷⁾ with MgSt ³⁷ Vd [Al], [A-2], [A-3], [A-4] and [A-5] [ 359] M-DHP-2 ⁴⁷⁾ with Hytal ⁷⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [360] M-DHP-2 ^{47 )} with naza ¹⁰⁾ and [Al], [A-2], [A-3], [A-4] and [A-5]

[361] M-DHP-2 ⁴⁷⁾ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [361a] M-DHP-2 ⁴⁷⁾ with c-HEXDGE ^29a) and [AI], [A-2], [A-3], [A-4] and [A-5] [362] M-DHP-2 ⁴⁷⁾ with BADGE ²⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [363] M-DHP-2 ⁴⁷⁾ with BFDGE ²⁶⁾ and [AI], [A- 2], [A-3], [A-4] and [A-5] [364] M-DHP-2 ⁴⁷⁾ with Glydi ³⁰⁾ and [Al], [A-2], [A-3] , [A-4] and [A-5] [365] M-DHP-2 ⁴⁷⁾ with Glytri ³¹⁾ and [Al], [A-2], [A-3], [A-4] and [ A-5] [366] M-DHP-2 ⁴⁷⁾ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [367] M -DHP-2 ⁴⁷⁾ with DCN ²⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [368] M-DHP-2 ⁴⁷⁾ with Mel ²³⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [369] M-DHP-2 ⁴⁷⁾ with ACEGA ²⁴⁾ and [AI], [ A-2], [A-3], [A-4] and [A-5] [370] M-DHP-2 ⁴⁷⁾ with TEPC ³²⁾ and [AI], [A-2], [A- 3], [A-4] and [A-5] [371] M-DHP-2 ⁴⁷⁾ with Cardura ³⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] where [352], [353], [361], [361a] and [368] are most preferred. Highlighted here are the combinations with [AI].

[372] P-DHP ⁵⁴⁾ with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [373] P-DHP ^{54 )} with CaH (c) ⁶⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [374] P-DHP ⁵⁴⁾ with MgH ^π) and [ Al], [A-2], [A-3], [A-4] and [A-5] [375] P-DHP ⁵⁴ with CaAcac ¹²⁾ and [Al], [A-2], [ A-3], [A-4] and [A-5] [376] P-DHP ⁵⁴ with MgAcac ¹³⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [377] P-DHP ⁵⁴⁾ with CaSt ³⁸⁾ and [Al], [A-2], [A-3], [A-4], and [A-5] [378] P -DHP ⁵⁴⁾ with MgSt ³⁷ Wd [Al] ₅ [A-2], [A-3], [A-4] and [A-5] [379] P-DHP ⁵⁴⁾ with Hytal ⁷⁾ and [Al ], [A-2], [A-3], [A-4] and [A-5] [380] P-DHP ^{S4) with} NaZA ¹⁰⁾ and [AI], [A-2], [A- 3], [A-4] and [A-5] [381] P-DHP ⁵⁴⁾ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4] and [ A-5] [381a] P-DHP ⁵⁴⁾ with c-HEXDGE ^29a) and [AI], [A-2], [A-3], [A-4], and [A-5] [382] P-DHP ⁵⁴⁾ with BADGE ²⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [383] P-DHP ⁵⁴⁾ with BFDGE ²⁶⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [384] P-DHP ⁵⁴⁾ with Glydi ³⁰⁾ and [AI], [A- 2], [A-3], [A-4] and [A-5] [385] P-DHP ⁵⁴ with Glytri ^3I) and [AI], [A-2], [A-3], [ A-4] and [A-5] [386] P-DHP ⁵⁴⁾ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] [387] P-DHP ⁵⁴⁾ with DCN ²⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [388] P-DHP ⁵⁴⁾ with Mel ²³⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [389] P-DHP ⁵⁴⁾ with ACEGA ²⁴⁾ and [AI], [A- 2], [A-3], [A-4] and [A-5] [390] P-DHP ⁵⁴⁾ with TEPC ³²⁾ and [AI], [A-2], [A-3], [ A-4] and [A-5] [391] P-DHP ⁵⁴ with Cardura ³⁵⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] with [372], [373], [381], [381a] and [388] being most preferred. Highlighted here are the combinations with [AI].

[392] Naf ⁴ ^ with CaH (u) ⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [393] Naf ⁴ ^ with CaH ( c) ⁶⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [394] Naf ⁴ ^ with MgH ^{1 υ} and [AI], [A- 2], [A-3], [A-4], and [A-5] [395] Naf ⁴⁵³ with CaAcac ¹²⁾ and [Al], [A-2], [A-3], [A-4 ] and [A-5] [396] Naf ^ with MgAcac ¹ ^ and [AI], [A-2], [A-3], [A-4] and [A-5] [397] Naf ⁴ ^ with CaSt ³⁸⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [398] Naf ⁴ ^ with MgSt ³⁷⁾ and [Al], [A- 2], [A-3], [A-4] and [A-5] [399] Naf ⁴ ^ with Hytal ⁷⁾ and [AI], [A-2], [A-3], [A- 4] and [A-5] [400] Naf ^ with NaZA ¹⁰⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [401] Naf ⁴ ^ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [401a] Naf ⁴ ^ with c-HEXDGE ^29a) and [AI], [ A-2], [A-3], [A-4], and [A-5]

[402] Naf ⁴ ^ with BADGE ²⁵⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [403] Naf ⁴⁵⁵ with BFDGE ²⁶⁾ and [AI] , [A-2], [A-3], [A-4], and [A-5] [404] Naf ⁴⁵⁾ with Glydi ³⁰⁾ and [Al], [A-2], [A-3] , [A-4] and [A-5] [405] Naf ⁴ ^ with Glytri ³¹⁾ and [Al], [A-2], [A-3], [A-4], and [A-5] [406] Naf ⁴ ^ with ESBO ⁵⁷⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [407] Naf ⁴ ^ with DCN ²⁰⁾ and [ Al] ₅ [A-2], [A-3], [A-4] and [A-5] [408] Naf ⁴ ^ with Mel ²³⁾ and [Al], [A-2], [A- 3], [A-4] and [A-5] [409] Naf ⁴⁵ * with ACEGA ²⁴⁾ and [AI], [A-2], [A-3], [A-4] and [A-4]. 5] [410] Naf ⁴ ^ with TEPC ³²⁾ and [AI] ₅ [A-2], [A-3], [A-4] and [A-5] [411] Naf ⁴⁵⁾ with Cardura ³⁵⁾ and [AI], [A-2], [A-3], [A-4], and [A-5] with [392], [393], [401], [401a] and [408] being most preferred. Highlighted here are the combinations with [AI].

[412] Hyd ⁵⁶⁾ with CaH (u) ⁵⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [413] Hyd ⁵⁶⁾ with CaH ( c) ⁶⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [414] Hyd ⁵⁶⁾ with MgH ^U) and [Al], [A- 2], [A-3], [A-4] and [A-5] [415] Hyd ⁵⁶⁾ with CaAcac ¹²⁾ and [Al], [A-2], [A-3], [A- 4] and [A-5] [416] Hyd ⁵⁶⁾ with MgAcac ¹³⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [417] Hyd ⁵⁶⁾ with CaSt ³⁸⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [418] Hyd ⁵⁶⁾ with MgSt ³⁷ Wd [Al], [A -2], [A-3], [A-4] and [A-5] [419] Hyd ⁵⁶⁾ with Hytal ⁷⁾ and [Al] ₅ [A-2], [A-3], [A -4] and [A-5] [420] Hyd ⁵⁶⁾ with NaZA ¹⁰⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [421] Hyd ⁵⁶⁾ with HEXDGE ²⁹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [421a] Hyd ⁵⁶⁾ with c-HEXDGE ^29a) and [AI ], [A-2], [A-3], [A-4] and [A-5] [422] Hyd ⁵⁶⁾ with BADGE ²⁵⁾ and [AI], [A-2], [A-3 ], [A-4] and [A-5] [423] Hyd ⁵⁶⁾ with BFDGE ²⁶⁾ and [AI], [A-2], [A-3], [A-4] and [A-5 ] [424] Hyd ⁵⁶⁾ with Glydi ³⁰⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [425] Hyd ⁵⁶⁾ with Eq ytri ³¹⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [426] Hyd ⁵⁶⁾ with ESBO ⁵⁷⁾ and [AI], [A-2 ], [A-3], [A-4] and [A-5] [427] Hyd ⁵⁶⁾ with DCN ²⁰⁾ and [Al], [A-2], [A-3], [A-4 ] and [A-5] [428] Hyd ⁵⁶⁾ with Mel ²³⁾ and [Al], [A-2], [A-3], [A-4] and [A-5] [429] Hyd ^{56 )} with ACEGA ²⁴⁾ and [AI], [A-2], [A-3], [A-4] and [A-5] [430] Hyd ⁵⁶⁾ with TEPC ³²⁾ and [AI], [A -2], [A-3], [A-4] and [A-5] [431] Hyd ⁵⁶⁾ with Cardura ³⁵⁾ and [AI], [A-2], [A-3], [A -4] and [A-5] where [412], [413], [421], [421a] and [428] are most preferred. Highlighted here are the combinations with [AI].

Of course, one or more AFVs may be combined with one or more SCVs and one or more [A].

Named are the following combinations, which are very particularly preferred:

8. Mixtures of (B-I) with (E) / CaH or CaSt and [A-I]

und [A-I] [434] DMAU⁴³⁾ mit Mel²³⁾/CaSt³⁸⁾ und [A-I] oder[432] DMAU ⁴³⁾ with Mel ²³⁾ / CaH (u) ⁵⁾ and [AI] [433] DMAU ⁴³⁾ with

and [AI] [434] DMAU ⁴³⁾ with Mel ²³⁾ / CaSt ³⁸⁾ and [AI] or

und [A-I][435] M-DHP-2 ⁴⁷⁾ with

and [AI]

In soft PVC, combinations of TEAP with 1,4-cyclohexanedimethanol diglycidyl ether [118b] are most preferred. Aminocrotonic acid esters and dihydropyridines are particularly suitable as initial color improvers.

Use of (A) as Antistatic or Antistatic Components (AS)

EP 0 751 179 A1 describes alkali metal perchlorates and triflates as antistatic components. They work in the presence of polyglycol mono-fatty acid esters. A disadvantage is the limited solubility of these salts in said esters. Surprisingly, it has been found that the inner complexes (A) according to the invention have a very good solubility and unfold good antistatic properties.

Examples of polymer substrates are: PVC-hard, PVC-soft, PVC-hard, CPVC, CPE, PVDC, HDPE, LDPE, PP, PS, HIPS ₅ PU, PA, PC, PET, PBT, TPU, PMMA, PVA, ABS, SAN ₅ MBS ₅ MABS, NBR, NAR, EVA ₅ ASA, and EPDM.

The following systems are used as additional components to (A): glycerol ether and / or ester R ⁸ OCH ₂ CH (OH) CH ₂ OH or R ⁸ CO ₂ CH ₂ CH (OH) CH ₂ OH and / or a DEA- derivative R ⁹ - [C (O)] _d -N (C ₂ H ₄ OH) ₂ or R ⁸ OCH ₂ CH (OH) CH ₂ - [C (O)] _d - N (C ₂ H ₄ OH) ₂ or R ⁹ N ((CH ₂ ) ₂ ) OH) - (CH ₂ ) ₃ - [C (O)] _d -N (C ₂ H ₄ OH) ₂ and / or a paraffin sulfate (or sulfonate) salt C ₁₂ -C ₁₈ -alkyl- (O) _d -SO ₃ Na ₅ Li ₅ K and / or a polyoxyalkylene of the formula (F)

R ^{8 is} -O- [CH (R ¹⁰ ) -CH ₂ -O-] _a - [CH ₂ - [CH (OH)] _b --CH ₂ -O] _c - [C (O)] _{d "} - R ⁹

(F)

With

Each R ⁸ independently = H ₅ C ₁ -C ₂₄ alkyl, C ₂ - C ₂₄ alkenyl, CH ₂ = CH-C (O) or CH ₂ = CCH ₃ -C (O);

Each R ⁹ independently = C ₁ -C ₂₄ alkyl, C ₂ - C ₂₄ alkenyl, (CH _{2) 2} OH, CH ₂ -COOH or N (C ₁ - C ₈ -alkyl) ₃ Hal; R ¹⁰ = H or CH ₃ , Hal = Cl, Br or I; a = an integer greater than or equal to 2, b = an integer from 1 to 6, and c, d, d ', d "independently = 0 or 1.

If substituents in the compounds of the formula (F) are alkyl having 1 to 24 carbon atoms, radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, Octadecyl, eicosyl, docosyl and tetracosyl and corresponding branched isomers in question.

If substituents in the compounds of the formula (F) are alkenyl having 1 to 24 carbon atoms, these radicals are derived from the abovementioned alkyl radicals, with the double bond preferably being arranged in the middle of the hydrocarbon chain. As alkenyl radical, oleyl is particularly preferred. When d is 1, R ⁹ as alkenyl is preferably also CH ₂ = CH- or CH ₂ = CCH ₃ -.

In the compounds of the formula (F), R is preferably H or C ₁ -C ₄ -alkyl and very particularly preferably H.

In the compounds of formula (F) R ⁹ is preferably C ₆ - C _2NC alkyl, C ₆ - C ₂₀ - alkenyl, or N (C ₁ - C ₈ alkyl) ₃ Cl, and most preferably C ₆ - C ₂₀ - alkyl or C ₆ - C ₂ o-alkenyl.

In the compounds of the formula (F), Hal preferably denotes Cl.

In the compounds of the formula (F), a is preferably a number between 2 and 20 and very particularly preferably a number between 2 and 14.

In the compounds of the formula (F), b is preferably a number between 2 and 6 and very particularly preferably the number 4.

In the compounds of the formula (F), c is preferably the number 0 or 1 and very particularly preferably c is the number 0 and d is the number 1. Particular preference is given to polypropylene glycol telluryl esters, polypropylene glycol oleate esters, polypropylene glycol methyl diethyl ammonium chloride, polyethylene glycol monomethyl ether, polyethylene glycol collauryl ester, polyethylene glycol olefin ester, polyethylene glycol olefin ether, polyethylene glycol sorbitan araolauryl ester, polyethylene glycol stearyl ester, polyethylene glycol polypropylene glycol telluryl ether and polyethylene glycol telluryl ether carboxylic acid.

Very particular preference is given to polyethylene glycol oleyl ethers and especially to polyethylene glycol telluryl esters.

Very particularly preferred are compounds of formula (F) wherein R ⁸ = H, R ⁹ = C ₆ - C ₂ o-alkenyl, R ¹⁰ = H or CH _3, a is a number between 2 and 14, c is zero and d is one is.

Examples of these are glycerol monolauryl, oleyl, palmitoyl and stearyl ethers; Glycerol monolaurate, oleate, palmitate and stearate; Lauryl, oleyl, palmityl and stearyldiethanolamine; Polyethylene glycol (PEG) monolaurate, monooleate, monopalmitate and monostearate, PEG monolauryl, myristyl, palmitate, stearyl and oleyl ethers. Oleic, palmitic and stearic acid diethanolamide. Sodium, potassium, lithium tetra, hexa and octa decanesulfonate or sulfate.

As commercial products may be mentioned: Dehydat ^® 10 ₅ Dehyd AT ^® R80X, IRGASTAT P ^®, ATMER ™, Lankrostat LA3 ^{®, ®} Ethoduomeen T / 12, Ethomeen ^® HT / 12, Ethomeen ^® T / 12, Ethomeen ^® 0/12, Ethomeen ^® C / 12, TEGIN ^® R90 and NOROPLAST ^® 2000.

Other important performance enhancers are phosphites and hindered amines.

phosphites

Organic phosphites are known co-stabilizers for chlorine-containing polymers. Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl,

Triphenyl, trilauryl, tricresyl, tris-nonylphenyl, tris-2,4-t-butyl-phenyl or

Tricyclohexyl. Further suitable phosphites are differently mixed aryldialkyl or alkyldiaryl phosphites, such as phenyldioctyl, phenyldidecyl, phenyldidodecyl,

Phenylditridecyl, phenylditetradecyl, phenyldipentadecyl, octyldiphenyl, decyldiphenyl, undecyldiphenyl, dodecyldiphenyl, tridecyldiphenyl, tetradecyldiphenyl,

Pentadecyldiphenyl, oleyldiphenyl, stearyldiphenyl and dodecyl-bis-2,4-di-t-butyl phenyl phosphite. Furthermore, it is also possible to use phosphites of various diols or polyols, for example tetraphenyldipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, tetraisodecyldipropylene glycol diphosphite, tris-dipropylene glycol phosphite, tetramethylolcyclohexanol-decyldiphosphite, tetramethylolcyclohexanolbutoxy-ethoxy-ethyldiphosphite, tetramethylolcyclohexanol-nonylphenyl diphosphite, bis-nonyl-phenyl-di-trimethylolpropane diphosphite, bis-2-butoxyethyl-di-trimethylolpropane diphosphite, trishydroxyethylisocyanurate hexadecyltriphosphite, didecylpentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis-2,4-di-t-butylphenylpentaerythritol diphosphite, and mixtures of these phosphites and Aryl / alkyl phosphite mixtures of statistical composition (H ₁₉ C ₉ - C ₆ H ₄ ) Oi ₁₅ P (OCi ₂₁ I ₃ H ₂₅ ^ ₇ ) W or (C ₈ H ₁₇ -C ₆ H ₄ -O-) ₂ P (iC ₈ H ₁₇ O), (H ₁₉ C ₉ -

C ₆ H ₄₎ O _{1; 5} P (OC H _{9jll 19; 23) LJ5.} Technical examples are Naugard P, Mark CH300, Mark CEBO1, Mark CH302 and Mark CH55 (manufactured by Crompton Co., USA). The organic phosphites may be used in an amount of, for example, 0.01 to 10, preferably 0.05 to 5 and especially 0.1 to 3 parts by weight, based on 100 parts by weight of PVC.

Sterically hindered amines (HALS)

The sterically hindered amines are generally compounds containing the group

\ / ^V

(G-I)

wherein A and V independently of one another are C ₈ alkyl, C ₃ - ₈ alkenyl, C _5-8 -

Cycloalkyl, or C ₇ - ₉ phenylalkyl, or together optionally replaced by O, NH or CH ₃ -N interrupted C ₂ - ₅ form alkylene, or a cyclic sterically hindered amine, in particular a compound from the series of the alkyl - or polyalkylpiperidines, especially the tetramethylpiperidines containing the group

(G-2)

Examples of such polyalkylpiperidine compounds are the following (in the case of the oligomeric or polymeric compounds, n and r in the range 2-20O _{5 are} preferably in the range 2-10, in particular 3-7):

01) N, N'-bis (2 ₅ 2,6,6-tetramethylpiperidin-4-yl) -ethylene-l, 2-di-acetamide

01a) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6-di-acetamide

01 b) N, N'-bis (2 ₅ 2,6,6-tetramethylpiperidin-4-yl) -ethylene 1, 2-di-formamide

02) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) adipamide

03) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -oxamide

04) 4-Hydroxybenzoesäureamido-2,2 ₅ 6,6-tetra-methylpiperidine

17)

There are also compounds of the following structure (G-3) in question:

(G-3)

Examples of compounds of formula (G-3) are:

Explanations :

Me = methyl;

Et = ethyl; Pr = propyl; Bu = butyl.

Other candidate compounds are: (N = 2-10)

n= 2-10

n = 2-10

n=2-10

n = 2-10

n=2-10

n = 2-10

Polymer aus:

Polymer from:

1

Further examples are:

121) ISO

Pr ₂ N-CH ₂ CH ₂ -NH-CO-CH ₂ CH ₂ -I ₂

122) so Pr ₂ N-CH ₂ CH ₂ CH ₂ -NH-CO-I ₂

128) tert Bu ₂ NC ₃ H ₆ -NH) ₂ CO

130) t ₂ NC ₂ H ₄ -NH-CO-) 2

133) ¹⁵⁰ Pr ₂ NC ₂ H ₄ -NH-CO-CH (OH) I ₂

134) (Et ₂ NC ₃ H ₆ -N (CH ₃ ) -CO-CH ₂ -) ₂

135) ^lso Pr'NC ₃ H ₆ -) ₂ N-CO-CH 3

137)

and compounds of structure (G-4)

(G-4)

Examples of compounds of the formula (G-4) are:

Where Me = methyl, Bu = butyl, ^tert Bu = tertiary-butyl, ^iso Pr = isopropyl, ⁿ Pr = normal-propyl, Ac = acetyl

As well as NOR-HALS compounds with the group

(G-5) wie

(G-5) like

mit R' = CH₃, n-C₄H₉, oder C-C₆H₁₁ with R '= CH ₃ , nC ₄ H ₉ , or CC ₆ H ₁₁

with R '= CH ₃ , nC ₄ H ₉ , or CC ₆ H ₁₁

mit R' = CH₃, n-C₄H₉, oder C-C₆H₁1

with R '= CH ₃ , nC ₄ H ₉ , or CC ₆ H ₁ 1

n= 2-10 mit R' = CH₃, n-C₄H₉, oder C-C₆H₁₁

n = 2-10 with R '= CH ₃ , nC ₄ H ₉ , or CC ₆ H ₁₁

n= 2-10 mit R' = CH₃, U-C₄H₉, oder C-C₆H₁₁

n = 2-10 with R '= CH ₃ , UC ₄ H ₉ , or CC ₆ H ₁₁

156) TINUVIN ^® NOR 371 FF

157) TINUVIN ^® XT 833

158) TINUVIN ^® XT 850

Preferred are triazine-based NOR-HALS compounds.

Further preferred are the compounds 1, Ia, Ib, 3, 4, 6, 9, 16, 41, 87, 88, 91, 92, 93, 103, 106, and 111.

Particularly preferred are 1, Ib, 2, 6, 9, 16, 41, 87, 88, 92, 93, 103, 111, 151, 152, 153, 154, 155 and 156, 157, 158.

Most preferred are 41, 87, 93, 103, 151, 152, 154, 156 and 157.

The compounds of components (G-1) - (G-5) are used for stabilization in the chlorine-containing polymer advantageously from 0.01 to 10, preferably from 0.05 to 5, in particular from 0.1 to 3 parts per 100 parts of polymer.

Instead of a single sterically hindered amine, a mixture of various sterically hindered amines can also be used in the context of the present invention. The amines mentioned are frequently known compounds; many of them are commercially available. The compounds may be present in the polymer at 0.005 to 5, preferably at 0.01 to 2 and especially at 0.01 to 1%.

A further preferred subject of the invention are mixtures of glycidyl compound (D) or cyanamide (E) -in particular melamine- with at least one stabilizer component (A), with at least one further co-component (BI), (B-2), (CI) and (C-2) to which is additionally added an HCl scavenger, preferably coated or uncoated calcium hydroxide and optionally another co-component (GI) or (G-2) or an antistatic component (F). Alternatively, systems containing (A) and scavengers are also preferred. These systems are mainly used for basic stabilization. Additional additives can be added to these mixtures.

Polyols and disaccharide alcohols, β-diketones, thiophosphites and thiophosphates, mercaptocarboxylic acid esters, hydroxycarboxylate metal salts, fillers, lubricants, plasticizers, pigments, antioxidants, UV absorbers, light stabilizers, optical brighteners, propellants, antistatics, are preferred as further component groups. Biocides (antimicrobials), antifogging agents, toughening modifiers, processing aids, gelling agents, flame retardants, metal deactivators and compatibilizers.

In addition, other additives such as adhesives, calendering aids, form (release agents), lubricants and fragrances and colorants may also be present. Examples of such additional components are listed and discussed below (see "Handbook of PVC Formulating" by E.J. Wickson, John Wiley & Sons, New York 1993).

Polyols and sugar alcohols

Examples of compounds of this type are: pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trimethylolpropane, sorbitol, maltitol, isomaltitol, lycasin, mannitol, lactose, leucrose, tris (hydroxyethyl) isocyanurate, palatinit, Tetra- methylcyclohexanol, tetramethylolcyclopentanol, tetramethylolpyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-O-o-C-D-glycopyranosyl-D-mannitol dihydrate. Preference is given to disaccharide alcohols. Also used are polyol syrups such as sorbitol, mannitol and maltitol syrups. The polyols may be in an amount of, for example, 0.01 to 20, suitably from 0.1 to 20 and in particular from 0.1 to 10 parts by weight, based on 100 parts by wt. PVC are used.

β-Diketones Useful 1,3-dicarbonyl compounds are linear or cyclic dicarbonyl compounds. Dicarbonyl compounds are preferably of the formula R ^{^} ₁ CHR ₂ CO - COR ^Λ related _3, wherein R ^{^} _{1 is} C ₁ -C ₂₂ - alkyl, C ₅ -C ₁₀ hydroxyalkyl, C ₂ -C ₁₈ alkenyl, phenyl, substituted by OH, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen-substituted phenyl, C ₇ -C ₁₀ -phenylalkyl, C ₅ -C ₁₂ -cycloalkyl, C ₁ -C ₄ -alkyl-substituted C ₅ -C ₁₂ - Cycloalkyl or a group -RyS-R ^{^} ₆ or -R> OR ^Λ ₆ ; R ^Λ _{2 is} hydrogen, C _r C ₈ alkyl, C ₂ -C ₁₂ alkenyl, phenyl, C ₇ -C ₁₂ alkylphenyl, C ₇ -C _{j0 phenylalkyl} or a group -CO-R ^{^} ₄ ; R _"3 has one of the meanings given for R'i or C ₁ -C ₁₈ -alkoxy, R _{'4 is} C ₁ -C ₄ -AhCyI or phenyl; R ^{^} ₅ Ci-Cio-alkylene and K ₆ Ci- Ci ₂ alkyl, phenyl, C ₇ -C ₁₈ alkylphenyl or C ₇ -C ₁₀ phenylalkyl.

These include the hydroxyl-containing diketones PS - EP 0 346 279 A1 and the oxa- and thiadiketones in PS-EP 0 307 358 A1 as well as the isocyanic acid-based ketoesters in PS-US 4,339,383.

R ^{^} ₁ and R ^{^} ₃ as alkyl may be in particular C 1 -C ₁₈ -alkyl, for. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl. R ^{^} ₁ and R _'3 as hydroxyalkyl are in particular a group - represents (CH _{2) n} -OH, wherein n is 5,

6 or 7 is.

R ^{^} ₁ and R _"2 Alkenyl can mean, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.

R ^{^} ₁ and R _'3 when substituted by OH, alkyl, alkoxy or halogen can examples game, tolyl, xylyl, tert be butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.

R ^{^} ₁ and R ^Λ ₃ as phenylalkyl are in particular benzyl. R ' ₂ and R " ₃ as cycloalkyl or alkylcycloalkyl are in particular cyclohexyl or methylcyclohexyl. R ' ₂ as alkyl may in particular be C ₁ -C ₄ -alkyl. R _"2 as C ₂ -C ₁₂ -alkenyl can in particular be allyl. R ^Λ ₂ as alkylphenyl can in particular be tolyl. _R'2 as phenylalkyl can in particular be benzyl. Preferably, R _'2 is hydrogen. R ₃ as alkoxy can for example ^Λ Methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy R's as Q-Qo-alkylene is in particular C ₂ -C ₄ -alkylene R ₆ as alkyl is in particular C ₄ -C ₁₂ -alkyl , z. For example, butyl, hexyl, octyl, decyl or dodecyl.

R ' ₆ as alkylphenyl is in particular tolyl. R ^Λ ₆ as phenylalkyl is in particular benzyl.

Examples of 1,3-dicarbonyl compounds of the above general formula and their alkali, alkaline earth and zinc chelates are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptanedione-2,4, benzoylacetone, dibenzoylmethane, Lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane, 5-hydroxycapronylbenzoylmethane, tribenzoylmethane, bis (4-methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-

Methoxybenzoylbenzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane, bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, biscyclohexanoylmethane, Di-pivaloyl-methane, 2-acetylcyclopentan-pentanone, 2-benzoylcyclopentanone, methyl, ethyl and diarylacetate, benzoyl, propionyl and butyryl-acetoacetic acid methyl and ethyl ester, triacetylmethane, methyl acetoacetate, ethyl, hexyl, octyl, dodecyl or octadecyl ester, methyl, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl benzoylacetate, and propionyl- and butyrylacetic acid -C ^ alkyl esters. Stearoylessigsäureethyl-, propyl, butyl, hexyl or -octylester and polynuclear ß-ketoester as described in PS - EP-A-0 433 230 and dehydroacetic acid and their zinc, magnesium or alkali metal salts. Preferred are Ca, Mg and Zn salts of acetylacetone and dehydroacetic acid.

Particularly preferably, 3-diketo compounds of the above formula wherein R ^{^} ₁ are C ₁ -C ₁₈ 1 - alkyl, phenyl, substituted by OH, methyl or methoxy, C ₇ -C ₁ o-phenylalkyl or cyclohexyl, R ' _{2 is} hydrogen and R " _{3 has} one of the meanings given for R ^{^} _1. This also includes heterocyclic 2,4-diones such as N-phenyl-3-acetylpyrrolidine-2,4-dione. Further representatives of this category are described in PS. EP 0,734,414 A1 The 1,3-diketo compounds may be used in an amount of, for example, from 0.01 to 10, Suitably 0.01 to 3 and in particular 0.01 to 2 parts by weight, based on 100 parts by weight of PVC, are used.

Thiophosphites and thiophosphates Thiophosphites or thiophosphates are understood to be compounds of the general type (RS) ₃ P, (RS) ₃ P =O or (RS) ₃ P =S, as described in the publications PS.

DE 28.09.492 Al, EP 0,090,770 A1 and EP 0,573,394 A1. Examples of these compounds are trithiohexyl phosphite, trithiooctyl phosphite, trithiolauryl phosphite, trithiobenzyl phosphite, trithiophosphoric acid tris (carbo-i-octyloxy) methyl ester. Trithiophosphoric acid tris (carbo-trimethylcyclohexyloxy) methyl ester, trithiophosphoric acid S, S, S-tris- (carbo-i-octyloxy) -methyl ester, trithiophosphoric acid S, S, S-tris- (carbo-2-ethylhexyloxy ) methyl ester, trithiophosphoric acid S, S, S-tris-1- (carbohexyloxy) -ethyl ester, trithiophosphoric acid S, S, S-tris-1 - (carbo-2-ethylhexyloxy) -ethyl ester, trithiophosphoric acid S, S, S-tris-2- (carbo-2-ethylhexyloxy) ethyl ester.

Mercaptocarboxylic ester

Examples of these compounds are esters of thioglycolic acid, thiomalic acid, mercaptopropionic acid, the mercaptobenzoic acids or of thiolactic acid, mercaptoethyl stearate and oleate, as described in the publications PS - FR-A 2,459,816, EP 0,090,748 A1 ₅ FR -A 2,552,440, EP 0 365 483 Al. The mercaptocarboxylic esters also include polyol esters or their partial esters.

Hydroxycεtrboxylatmetallsalze

Furthermore, hydroxycarboxylate metal salts may be present, wherein the metal may be an alkali or alkaline earth metal or aluminum. Preference is given to sodium, potassium, magnesium or calcium. The hydroxycarboxylic acid can be glycolic, lactic, malic, tartaric or citric acid or salicylic or 4-hydroxybenzoic acid or also glycerol, gluconic and sugar acids (see, for example, PS-GB 1,694,873 and EP .303,564 A1).

Furthermore, other layered lattice compounds such as Li-hydrotalcite can be used. Further details can be found in PS - EP 0.930.332 A1. The synthesis of L-CAM perchlorate is described, for example, in PS EP 0,761,756 A1.

Fillers Examples include calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, china-gay, talc, glass fibers, glass beads, wood flour, mica, Metal oxides or metal hydroxides, carbon black, graphite, rock flour, barite, glass fibers, talc, kaolin and chalk related. Preference is given to chalk (also coated) (HANDBOOK OF PVC FORMULATION EJ Wickson, John Wiley & Sons, 1993, pp. 393-449) and reinforcing agents (POCKET BOOK OF PLASTIC ADDITIVES, R. Gächter & H. Müller, Carl Hanser, 1990, p. 549-615).

The fillers may be used in an amount of preferably at least 1 part, for example 5 to 200, advantageously 5 to 150 and in particular 5 to 100 parts by weight, based on 100 parts by weight of PVC.

lubricant

Suitable lubricants are, for example: montan waxes, fatty acid esters, PE and PP waxes, amide waxes, chloroparaffins, glycerol esters or alkaline earth metal soaps, furthermore fatty ketones and combinations thereof, as listed in PS EP 0259.783 A1. Preference is given to calcium stearate.

softener

Suitable organic plasticizers are, for example, those from the following groups:

(i) phthalic acid esters, such as preferably di-2-ethylhexyl, di-isononyl and diisodecyl phthalate, which are also known under the common abbreviations DOP (dioctyl phthalate, di-2-ethylhexyl phthalate), DINP (diisononyl phthalate ), DIDP (diisodecyl phthalate) are known (ii) esters of aliphatic dicarboxylic acids, especially esters of adipic, azelaic and sebacic acid, preferably di-2-ethylhexyl adipate and di-iso-octyl adipate

gebräuchliche Abkürzungen sind TOTM (Trioctyltrimellitat, Tri-2-ethyIhexyl-trimellitat), TIDTM (Triisodecyltrimellitat) und TITDTM (Triisotridecyltrimellitat)(iii) trimellitic acid esters, for example tri-2-ethylhexyl trimellitate, triisodecyltrimellitate (mixture), triisopropyltrimellitate, triisoctyl trimellitate (mixture) and tri-C ₆ -C ₈ -alkyl, tri-iso-decyltrimellitate C ₆ -C ₁₀ alkyl, tri C ₇ -C ₉ alkyl and

common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyl trimellitate), TIDTM (triisodecyl trimellitate) and TITDTM (triisotridecyl trimellitate)

(iv) epoxy plasticizer; in the main, the epoxidized unsaturated fatty acids are, for example, epoxidized soybean oil (v) polymer plasticizers: The most common starting materials for their preparation are dicarboxylic acids such as adipic, phthalic, azelaic and sebacic acid; Diols like 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol, (s. AdmEx ^® grades of Velsicol Corp. and PX-811 of Asahi Denka) (vi) Phosphoric acid esters: A definition of these esters can be found in the above-mentioned "TASCHENBUCH DER KUNSTSTOFF ADDITIVE" chapter 5.9.5, pp. 408 - 412. Examples of such phosphoric acid esters are tributyl phosphate, tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethyl phosphate, 2-ethyl-hexyl-di-phenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and

® trixylenyl phosphate; preferred are tri-2-ethylhexyl phosphate and Reofos 50 and 95

(Ciba Specialty Chemicals) (vii) Chlorinated hydrocarbons (paraffins)

(viii) hydrocarbons

(ix) monoesters, e.g. Butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and

alkylsulfonic

(x) glycol esters, e.g. Diglycium zoates (xi) citric acid esters, e.g. Tributyl citrate and acetyltributyl citrate as in PS - WO

02/05206

(xii) perhydrophthalic, isophthalic and terephthalic esters and perhydroglycol and

® diglycol zoate ester; Preference is given to perhydro-diisononyl phthalate (hexamold DINCH -

BASF) as described in PS - DE 197.56.913 Al, DE 199.27.977 Al, DE 199.27.978 Al and DE 199.27.979 Al.

(xiii) castor oil-based plasticizer (Soft-N-Safe ^®, manufacturer. DANISCO)

(xiv) terpolymers ketone ethylene ester Elvaloy ^® KEE, (Elvaloy ^® 741, Elvaloy ^® 742,

Manufacturer Fa. DuPont)

A definition of these plasticizers and examples of such are in "TASCHENBUCH DER KUNSTSTOFFADDITIVE", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989, chapter 5.9.6, pages 412-415, as well as in "PVC TECHNOLOGY", WV Titov, 4 ^th . Ed., Elsevier Publ., 1984, pp. 165-170. It can also be used mixtures of different plasticizers. The plasticizers may be used in an amount of, for example, 5 to 50 parts by weight, suitably 10 to 45 parts by weight, based on 100 parts by weight of PVC. Hard or semi-hard PVC preferably contains up to 20%, more preferably up to 5% or no plasticizer.

Pigments Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are TiO ₂ , zirconia-based pigments, BaSO ₄ , zinc oxide (zinc white) and lithopone (Zinc sulfide / barium sulfate), carbon black, carbon black-titanium dioxide mixtures, iron oxide pigments, Sb ₂ O ₃ , (Ti, Ba, Sb) O _2; Cr ₂ O ₃ , spinels such as cobalt blue and cobalt green, Cd (S ₉ Se), ultramarine blue. Organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo-pyrrolopyrrole pigments and anthraquinone pigments. Preferably, TiO _{2 is} also in micronized form. A definition and other descriptions can be found in the "HANDBOOK OF PVC FORMULATION", EJWickson, John Wiley & Sons, New York, 1993.

Antioxidants These include hindered phenol, such as alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, e.g. As 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, eg. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), alkylidene bisphenols, e.g. 2,2'-methylenebis (6-tert-butyl-4-methylphenol), benzyl compounds, e.g. 3.5.3% 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, hydroxybenzylated malonates, e.g. Dioctadeoyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, hydroxybenzyl aromatics, e.g. l, 3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, triazine compounds, e.g. 2,4-bis-octyl-mercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, phosphonates and phosphonites, e.g. Dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acylamino-phenols, e.g. A-hydroxy-lauric acid anilide, esters of beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid , the beta- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, amides of the beta- (3,5 Di-tert-butyl-4-hydroxyphenyl) -propionic acid, eg N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, vitamin E (tocopherol) and derivatives, and D, L-ascorbic acid. The antioxidants may be used in an amount of, for example, from 0.01 to 10 parts by weight, advantageously from 0.1 to 10 parts by weight, and in particular from 0.1 to 5 parts by weight, based on 100 parts by weight of PVC become.

UV absorber and light stabilizer

Examples of these are benzotriazole derivatives, such as, for example, 2- (2'-hydroxyphenyl) -benzotriazole-1,2,3, for example 2- (2'-hydroxy-5'-methyl-phenyl) -benzotriazole, 2- (2'-hydroxybenzoyl) 5'-methyl-phenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benztriazole, 2- (2'-hydroxybenzoyl) 3 ', 5'-di-tert-butyl-phenyl) -5-chloro-benztriazole. Further examples are 2-hydroxybenzophenones, esters of optionally substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds, oxalic acid diamides, eg 4,4'-dioctyloxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl- oxanilide, 2- (2-hydroxyphenyl) -1, 3,5-triazines, eg 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy 4-octyloxyphenyl) -4,6-bis (2,4-dikhyl-phenyl) -l, 3,5-triazine, sterically hindered amines based on tetramethylpiperidine or tetramethylpiperazinone or tetramethylmorpholinone, eg bis (2,2, 6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, and

Benzoxazinones such as 1,4-bis-benzoxazinonyl-benzene.

Optical brighteners

Examples of these are bis-benzene (1,4) -oxazoles, phenylcoumarins and bis-styryl-biphenyls such as 4-methyl-7-diemylaminocoumarin, 3-phenyl-7- (4-methyl-6-butoxybenzoxazole) -coumarin, 4 4'-bis (benzoxazol-2-yl) stilbene and 1,4-bis (-benzoxazol-2-yl) -naphthalene. Preference is given to solutions of optical brighteners in a plasticizer, for example DOP.

propellant

Propellants are e.g. organic azo and Hy drazo compounds, tetrazoles, oxazines, isatric anhydride, N-methylisatinic anhydride, and soda and sodium bicarbonate. Preference is given to azodicarbonamide and sodium bicarbonate and mixtures thereof. Very particular preference is given to isatric anhydride or N-methylisatinic anhydride, especially in soft PVC or semi-hard PVC.

antistatic agents

Antistatic agents are classified into nonionic (a), anionic (b), cationic (c) and amphoteric (d) classes. To (a) include fatty acid ethoxylates, fatty acid esters, ethoxylated fatty alkylamines, fatty acid diethanolamides and ethoxylated phenols and alcohols, and polyglycol monofatty acid esters. To (b) include alkali fatty bisulfonates and phosphoric acid bis-fatty alcohol ester alkali salts. (C) includes fatty alkyl quaternary ammonium salts and (d) includes fatty alkyl betaines and fatty alkyl imidazoline betaines. Individual preferred compounds are lauric diethanolamide, myristyl diethanolamine, sodium octadecyl sulfonate and Na bis-octadecyl phosphate. The presence of component (A) allows in many cases due to the inherent properties of a reduction in the amount of expensive antistatic agents.

Definitions and examples of other additives such as impact modifiers and processing aids, gelling agents, biocides, metal deactivators, flame retardants, Antifogging agents and compatibilizers are described in "HANDBUCH DER PLASTTOFFADDITIVE", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989, as well as 4th edition 2001 and in the "HANDBOOK OF POLYVINYL CHLORIDE FORMULATION" EJ Wickson, J. Wiley & Sons, 1993, and in "PLASTICS ADDITIVES" G. Pritchard, Chapman & Hall, London, Is Ed., 1998. Impact impact modifiers are further described in detail in "IMPACT MODIFIERS FOR PVC", JT Lutz / DL Dunkelberger, John Wiley & Sons, 1992.

Further stabilizers may be 2-phenylindole, 2-pyrrolecarboxylic acid (ester), 2,4-diphenylpyrrole and 2-alkyl-4-phenyl-pyrrole-3-carboxylic acid ester, and 3-amino-4-alkyl / phenyl-pyrrole-3 carbon ester (see EP 1.299.466 A1)

Also preferred are stabilizer systems which additionally contain a substituted indole or a

Contain urea or an aniline derivative. Examples of suitable compounds sin 2-phenyllaurylindole and N, N'-diphenylthiourea and phenylurea. Further

Examples are described in PS - DE 101.07.329 A1. See also PS -

EP 0,768,336 A1, EP 0174,412, EP 0,967,245 A1, EP 0,967,209 A1, EP 0,967,208 A1,

EP 0,962,491 A1, EP 1,044,968 A1, WO 02/072 684 and WO 02/048 249.

A particular preference lies in the combination of the blends (A) / (BI), (B-2), (CI), (C-2) + SCV or AS (especially (D), (E) and (F)) with phosphite esters, the additional phosphite distearylpentaerythritol diphosphite, triphenyl phosphite, tris-nonylphenyl phosphite, phenyldidecyl phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, tetraisodecyl (dipropylene glycol) diphosphite, tris-dipropylene glycol phosphite, decyl diphenyl phosphite, trioctyl phosphite, trilauryl phosphite or (nonylphenyh-Cn / Cn-alkyl ^ s-phosphite.

In the compositions according to the invention, the compounds of the general formulas (Bl / B-2) or (Cl / C-2) + SCV or AS are advantageously from 0.01 to 10, preferably from 0.05 to, in order to achieve stabilization in the chlorine-containing polymer 5, based on 100 parts by weight of polymer to use. The inner complexes (A) are used in an amount of, for example, 0.001 to 10, preferably 0.01 to 5, particularly preferably 0.01 to 3 parts by weight, based on 100 parts by weight of polymer. Preference is given to compositions in which the ratio of the compound of the general formulas (B) and (C) to the inner complexes (A) by weight is in the range from 4: 8: 1 to 6: 30: 1. Preferably, compositions containing 0.01 to 10 parts by weight of hindered amine and / or NOR-HALS compound (G1-G5) and / or UV absorber and / or titanium dioxide are included.

Preferred compositions contain, based on 100 parts by weight of chlorine-containing polymer, 0.01-10 parts by weight of compound (B) and 0.01-10 parts by weight of compound (C) per 0.001-1 part by weight of the inner complexes (A).

Examples of the chlorine-containing polymers to be stabilized are polymers of vinyl chloride, vinylidene chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, especially vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and acrylonitrile, copolymers of Vinyl chloride with diene compounds and unsaturated dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, postchlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, Vinyl isobutyl ether and the like; Vinylidene chloride polymers and copolymers thereof with vinyl chloride and other polymerizable compounds; Polymers of vinyl chloroacetate and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and alpha-substituted acrylic acid; Polymers of chlorinated styrenes, for example dichlorostyrene; Chlorinated rubbers; chlorinated polymers of ethylene; Polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride, chlorinated natural and synthetic rubbers, and mixtures of said polymers with each other or with other polymerizable compounds. In the context of this invention, PVC also means copolymers of vinyl chloride with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, which may be suspension, bulk or emulsion polymers.

Preference is given to a PVC homopolymer, also in combination with polyacrylates or polymethacrylates.

Also suitable are graft polymers of PVC with EVA, ABS and MBS, as well as graft polymers of PVC with PMMA. Preferred substrates are also mixtures of the abovementioned homopolymers and copolymers, in particular vinyl chloride homopolymers, with other thermoplastic or / and elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and Polylactones, in particular from the group ABS, NBR, NAR, SAN and EVA. The related abbreviations for the copolymers are familiar to the person skilled in the art and mean the following: ABS acrylonitrile-butadiene-styrene; SAN styrene-acrylonitrile; NBR acrylonitrile-butadiene; NAR acrylonitrile acrylate; EVA ethylene vinyl acetate. In particular, acrylate-based styrene-acrylonitrile copolymers (ASA) are also suitable. Preferred components in this context are polymer compositions which contain as components (i) and (ii) a mixture of 25-75% by weight of PVC and 75-25% by weight of the copolymers mentioned. Of particular importance as a component are compositions of (i) 100 parts by weight of PVC and (ii) 0-300 parts by weight of ABS and / or SAN-modified ABS and 0-80 parts by weight of the copolymers NBR, NAR and / or EVA, but especially EVA.

Also suitable for stabilization in the context of this invention are in particular recyclates of chlorine-containing polymers, which are the polymers described in greater detail above, which have suffered damage as a result of processing, use or storage. Particularly preferred is PVC recyclate. Another use of the stabilizer combinations according to the invention is that antistatic properties can be imparted to the finished article made of hard or soft PVC. In this way it is possible to reduce the use of expensive antistatic agents. Preferred for this application is soft PVC or semi-rigid PVC.

Another object of the present invention is a composition comprising plasticized PVC and a stabilizer system containing 1,4-cyclohexanedimethanol diglycidyl ether.

Another object of the invention are utility (utensils) containing PVC and inventive systems.

Preference is also the use of consumer goods, which are characterized by a special fine foam structure. This applies to hard, soft and semi-hard PVC.

This aspect is particularly important for wallpapers and floors made of soft PVC. Normally, heavy metal compounds such as Zn or Sn stabilizers are required as kickers to obtain a fine foam. Surprisingly, it has been found that TEA inner complexes exert a kicker effect on isatinic acid or N-methylisatic anhydride, which ensures the achievement of a fine foam structure.

It was also unpredictable that the electrical resistance properties of a consumer article containing TEA core complexes as a component are drastically improved, which proves to be particularly beneficial in cable and insulator manufacturing and semiconductor applications.

Furthermore, these products (mainly cables) perform better when stored in water, because the formulations do not contain zinc soaps and thus do not produce zinc chloride during processing, which deteriorates the electrical values after migration to the plastic surface.

In addition, zinc-containing fungicides can be added to zinc-sensitive applications primarily in the field of soft PVC (e.g., films, roofing membranes) in dire need of biocidal equipment, severely limiting the use of calcium-zinc stabilizers.

The co-usable compounds as well as the chlorine-containing polymers are generally known to the person skilled in the art and are described in detail in "HANDBUCH DER KUNSTOFFADDITIVE", R. Gächter / H. Müller, Carl Hanser Verlag, 3rd ed., 1989 and 4th ed. 2001, in PS - DE 197.41.778 A1 and EP 0.967.245 A1, to which express reference is hereby made.

The stabilization according to the invention is particularly suitable for chlorine-containing polymer compositions that are not plasticized or plasticizer-free or substantially plasticizer-free compositions, as well as for plasticized compositions. Particular preference is given to applications in rigid PVC or PVC semi-hard.

The compositions according to the invention are particularly suitable, in the form of hard formulations, for hollow bodies (bottles), packaging films (thermoformed films), blown films,

"Crash Pad" films (automobiles), pipes, foams, heavy profiles (window frames), Lightwall profiles, construction profiles, foils, blister packs (also produced by the Luvitherm method), profiles, sidings, fittings, office films, margarine cups, chocolate moldings and apparatus housings, insulators, computer housings and components of household appliances as well as for electronic applications, in particular in the semiconductor sector. These are particularly suitable for the production of window profiles with high whiteness and surface gloss.

Preferred other compositions in the form of semi-hard and soft formulations are for wire sheathing, cable insulation, decorative films, roofing foils, foams, agricultural films, hoses, sealing profiles, flooring, wallpaper, automotive parts, soft films, injection molded parts (blow molding), office films and Foils suitable for inflatable halls. Examples of the use of the compositions according to the invention as plastisols are toys (rotational molding), artificial leather, flooring, textile coatings, wallpaper, coil coatings and underbody protection for motor vehicles. Examples of sintered PVC applications of the compositions according to the invention are slush, slush mold and coil coatings and in E-PVC for films produced by the Luvithermverfahren. For details, see "PLASTICS MANUAL PVC", Volume 2/2, W. Becker / H. Braun, 2nd ed., 1985, Carl Hanser Verlag, p 1236-1277.

The components (A) and (B1) / (B-2) and / or (Cl) / (C-2) can be premixed together with other stabilizers or additives or PVC substrate, preferably as further stabilizers alkaline earth metal hydroxides, zeolites , Hydrotalcites, glycidyl compounds or melamine. Very special preference is given to so-called hot mixers which operate in a temperature range from 8O ⁰ C up to 120 ° C. Here, an optimal homogenization is achieved. In the presence of PVC powder, stabilizers and other additives diffuse into the PVC grain. A variant consists in that the mixing process in a lubricant melt, which may contain Ca-stearate or Mg-laurate or stearate or (Hy droxy) stearic acid, in the presence of a Ca or Mg hydroxide, a basic Mg, Ca- or Al-salt or of "overbased" compounds of magnesium and calcium or of a polyol or of a zeolite, where maltitol, lactitol, palatinite or zeolite A, Ca hydroxide, a basic Ca or Mg salt or an overbased compound of magnesium or calcium is preferred.

Particularly preferred is the embodiment in which in this melt the components (Bl) / (B-2) or / and (Cl) / (C-2) + SCV (in particular (D), (E) and Calcium hydroxide or melamine) are submitted and the component (A) is added, wherein the components (F) and (G) may be contained in the premix.

Advantageously, the incorporation of the stabilizers in another variant can be carried out by the following methods: as an emulsion or dispersion (a possibility is, for example, the

Form of a pasty mixture, an advantage of the system according to the invention is in this dosage form in the stability of the paste); as a dry mix during the

Mixing additional components or polymer blends; by direct addition to the processing apparatus (for example calender, mixer, kneader, extruder and the like) or as a solution or melt or as flakes or pellets in dust-free form as one-

Pack.

Particular preference is given to premixing of components (A) with (B1) / (B-2) or (C1) / (C-2) with SCV (in particular (D), (E) and calcium hydroxide or melamine) and optionally (F) or / and (G) in compacted form, prepared in granulation apparatus, whereby a non-dusting, non-sticky, free-flowing granules are obtained, which mixes with eg PVC and very easy to open during the processing process. It is of great advantage during manufacture (compacting or spraying) to add binders, which preferably consist of cellulose ethers or esters (mainly hydroxyethyl, hydroxypropyl and hydroxypropylmethylcellulose or carboxymethylcellulose). Alternatively, polyvinyl alcohol or polyvinylpyrrolidone may also be added.

In addition to wet granulation, preference is given to dry granulation which, in the presence of fatty-acidic Mg or Ca salts or metal-free lubricants based on esters or hydrocarbons, leads to non-dusting, free-flowing cylindrical granules. In the presence of lubricants, preferably ester waxes, melt granulation yields flakes, flakes or pastilles which are very readily dispersible in PVC.

The polymer stabilized according to the invention can be prepared in a manner known per se, for which purpose the stabilizer mixture according to the invention and optionally further additives are mixed with the polymer using devices known per se, such as the abovementioned processing apparatuses. Here, the stabilizers can be added individually or in mixture or in the form of so-called masterbatches. The stabilized polymer of the present invention can be brought into the desired shape in known manners. Such processes include, for example, milling, calendering, extruding, injection molding or spinning, as well as extrusion blowing. The stabilized polymer can also be made into foams. The invention thus also provides a process for stabilizing chlorine-containing polymers by adding the stabilizer mixture according to the invention to a chlorine-containing polymer, as well as objects containing PVC which is stabilized by the stabilizer mixtures according to the invention.

Another object of the invention is a process for the stabilization of chlorine-containing polymers by adding a stabilizer system according to the invention to a chlorine-containing polymer, in particular soft PVC or paste PVC. The soft PVC may be suitable for the production of floors, automotive parts, wall cladding, flexible films, hoses, injection molded parts or preferably for wire sheathing (cable). Alternatively, the chlorine-containing polymer may be a rigid PVC. The chlorine-containing polymer can also be used for the production of films (also Luvitherm), PVC pipes or profiles, preferably of window profiles.

The inner complexes according to the invention can be prepared in methanol, ethanol, propanol, triethanolamine or water, the solvent and any water of reaction being removed by distillation. The distillation residue can then be digested in a non-polar solvent and separated by filtration. Alternatively, the synthesis can be carried out in an alcohol and the reaction product then precipitated by the addition of a nonpolar solvent.

Examples

These explain the invention in more detail. Parts are, as in the rest of description, unless otherwise stated, by weight.

1. Synthesis examples

1.1 Triethanolamine perchlorato (triflato) internal complexes

1.1.1 TEA-Perchlorato-Sodium (TEAP) - [(TEA) Na (OClO ₃ )] In an 1L pear-shaped flask, add 35.2g of sodium perchlorate monohydrate (NaP _* H ₂ O, 0.25mol) and 37.3g of triethanolamine (TEA, 0.25 mol) dissolved in 100 ml of methanol. The Reaction mixture is concentrated on a rotary evaporator at 72 ° C (finally under vacuum) to dryness, wherein the water of hydration is removed. The anhydrous compound is obtained in crystalline form. The product obtained is i.Vak. dried. Yield 67g (quantitative), mp .: 131 ⁰ C (sharp).

It is also possible to use aqueous NaP solutions in which stoichiometric amounts of TEA dissolved in methanol, ethanol, isopropanol, THF, acetone or water are admixed. Another alternative is to use NaP (.H ₂ O) suspensions in organic solvents such as acetone, THF, glycol ethers (dimethoxyethane), isopropanol, dioxane, DMF, DMA, acetonitrile, etc.

The workup can also be modified by replacing the TEA inner complexes from o. Solutions can be precipitated in the form of tuft-shaped crystals by addition of non-polar solvents, such as ethyl acetate, hydrocarbons (aromatic or aliphatic), chlorinated hydrocarbons, ethers (MTBE) (see Fig. 1). These modifications can also be applied to the following examples.

1.1.2 Bis-TEA-perchlorato-calcium (TECAP) - [(TEA) ₂ Ca (OCIOs) ₂ ]

In an 1 L pear-shaped flask, 38.9 g of calcium perchlorate tetrahydrate (0.125 mol) and 37.3 g of triethanolamine (TEA, 0.25 mol) are dissolved in 100 ml of methanol. The reaction mixture is concentrated on a rotary evaporator at 72 ⁰ C (finally under vacuum) to dryness, wherein the water of hydration is removed. The anhydrous crystalline product is obtained. The resulting compound is i.Vak. dried. Yield 67 g (quantitative), mp:> 280-285 ° C. (decomposition dark coloration).

1.1.3 TEA Triflato Sodium (TEAT) - [(TEA) Na (OSO ₂ CF ₃ )]

In a 1 L pear-shaped flask, 43.0 g of sodium triflate (0.25 mol) and 37.3 g of triethanolamine (TEA ₅ 0.25 mol) are dissolved in 100 ml of methanol. The reaction mixture is concentrated on a rotary evaporator at 72 ⁰ C (finally under vacuum) to dryness, wherein the water of hydration is removed. The anhydrous crystalline product is obtained. The resulting compound is i.Vak. dried. Yield 80 g (quantitative) m.p .: 97 ⁰ C (unsharp). 1.1.4 Bis-TEA perchlorato zinc (TEZIP) - [(TEA) ₂ Zn (OClO ₃ ) ₂ ]

In a 1L pear-shaped flask, 4.7g zinc perchlorate hexahydrate (12.5mmol) and 3.7g triethanolamine (TEA, 25mmol) are dissolved in 20ml methanol. The reaction mixture is concentrated on a rotary evaporator at 72 ° C (finally under vacuum) to dryness, wherein the water of hydration is removed. The anhydrous crystalline product is obtained. The resulting compound is called i.Vak. dried. Yield 7.0 g sinter (quantitative), m.p .: from 80 ⁰ C glassy; 230-250 ⁰ C yellow to brown, liquid.

1.2. Dihydropyridine compounds (DHPs) ²⁾

1.2.1 4-Dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid dimethyl ester

(Mono-DHP)

In a 1L round-bottomed flask 73.5 g of methyl .beta.-aminocrotonate (MAC; 0,64mol) and 30 g of formalin (37%) (l, lmole) in 500 ml of isopropanol and stirred for Ih at 6O ⁰ C. The mixture is then heated at reflux for 6 h, forming a yellow solid. The suspension is then stirred into water and the precipitate is removed. This is washed with water, then with acetone and i.Vak. dried. Yield: 57.4 g (corresponding to 80% of theory), mp: 224-225 ° C

1.2.2 Bis- [1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid] -l, 4-butanediol diester (bis-DHP)

In a 1L round-bottomed flask, 64.1 g of 1,4-butanediol-bis-3-aminocrotonate (BAC;

0.25 mol) with 57,6g Methyl-.beta.-aminocrotonate (MAC; pure) dissolved in 500ml isopropanol, 0.5 mol) and 75 g of formalin (37% and stirred for Ih at 60 ⁰ C. The mixture is then heated at reflux for 6 h, forming a yellow solid. The suspension is then stirred into water and the precipitate is filtered off. This is with water, then with

Acetone washed and i.vak. dried.

Yield: 81g (corresp. With 73% of theory), mp .: 192-194 ⁰ C.

1.2.3 Bis- [1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid] thio-diethylene glycol diester (bis-thio-DHP)

In a 1L round bottomed flask, 72.1 g of thiodiglycol-bis-aminocrotonate (TAC, 0.25 mol) with 57.6 g of methyl β-aminocrotonate (MAC, 0.5 mol) and 75 g of formalin (37%) in 500 ml

²⁾ Based on PS-EP286887 Isopropanol dissolved and Ih stirred at 60 ⁰ C. The mixture is then heated at reflux for 6 h, forming a yellow solid. The suspension is then stirred into water and the precipitate is filtered off. This is washed with water, then with acetone and i.Vak. dried. Yield: 64,5g (corresp. With 56% of theory), mp. 148- 152 ⁰ C.

1.2.4 Poly [1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid] -l, 4-butanediol ester (poly-DHP)

In a 1L round bottomed flask, 76.4 g of 1,4-butanediol-bis-3-aminocrotonate (BAC; 0.298 mol) with 4.9 g of methyl β-aminocrotonate (MAC, 0.0426 mol) and 30 g of formalin (37%) are added. dissolved in 500 ml of isopropanol and Ih stirred at 60 ° C. The mixture is then heated at reflux for 6 h, forming a yellow solid. The suspension is then stirred into water and the precipitate is filtered off. This is washed with water, then with acetone and i.Vak. dried. Yield: 63.9 g (corresponding to 80% of theory), mp: 218-22O ⁰ C.

1.2.5 Poly- [1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid thiodiethylene glycol ester] (poly-thio-DHP)

In a 1 liter round bottom flask, 86.5 g of thiodiglycol bis-aminocratonate (TAC; 0.30 mol) are dissolved in 500 ml of isopropanol with 4.9 g of methyl β-aminocrotonate (MAC; 0.0426 mol) and 30 g of formalin (37%) Ih at 60 ⁰ C stirred. The mixture is then heated at reflux for 6 h, forming a yellow solid. The suspension is then stirred into water and the precipitate is filtered off. This is washed with water, then with acetone and i.Vak. dried. Yield: 76,3g (corresp. With 85% of theory), mp .: 168-170 ⁰ C.

2. Application examples 2.1 Dehydrochlorination (DHC) tests 2.1.1 Preparation of powder samples

5 or 10 g (corresponding to 100 phr) of PVC ^a) are introduced into an 1 L pear-shaped flask and the additives are added according to the table examples. The blends consist of 1.6 phr of HCl scavenger (SCV), 0.4 phr of initial color improver (AFV), and the appropriate amounts of TEAP booster (0.16 phr). Then you add 50ml Methanol and concentrated this slurry on a rotary evaporator at 72 ° C / vacuum to dryness. The resulting powder mixtures are homogenized in agate mortar. (The method is preferred for one or two liquid additives.) If all additives are solid, homogenization in the agate mortar alone can be carried out and the process of the MeOH slurry can be dispensed with.)

2.1.2 Performance of dehydrochlorination measurements

The DHC is a measure of the HCl elimination of PVC that occurs under thermal stress. The split-off hydrochloric acid is charged with nitrogen gas into a receiver with dist. Rinsed water and there measured the increase in conductivity in microsiemens per centimeter (μS / cm). The corresponding minute values (min) are used as key figures. The longer the time interval to reach a certain conductivity, the more thermostable is the PVC sample. Device type: PVC Thermomat 763 (Metrohm)

The measurements are carried out according to DN 53381 Part 1, Method B: Conductivity measurement.

Parameter: Sample weight: 500 ± 5mg

Temperature: 180 ° C flow: 7 l / h (nitrogen 5.0)

Absorption volume: 60ml (dem. Water)

Evaluation: t ₁₀ , t ₅ o and t ₂₀₀ (conductivity of 10, 50 and 200 μS / cm - in minutes)

Measurement: After weighing the powder samples into the reaction vessels, the measuring vessels are filled with deionised water and equipped with conductivity electrodes. After reaching the measuring temperature (180 ⁰ C), the sealed reaction vessels are transferred to the heating block, coupled via the corresponding hose connections with the measuring vessels and started the measurement. The stability criteria are the tio, t ₅ o and t2 ₀₀ values.

2.1.3 Examples

2.1.3.1 Effect of (A) as a singular PVC stabilizer (Tab.l)

Trial 1: 100 phr PVC ³⁾ without stabilizer (booster) Trial 2: 100 phr PVC ³⁾ + booster.

³⁾ Vinnolit S 3160, K value 60 Tab.l

It can be seen that the formulation according to the invention (experiment 2) has a drastic increase in the thermostabilization compared with unstabilized PVC (tio = 400%, t ₅₀ = 210% and t ₂₀₀ = 250%).

2.1.3.2 Effect of (A) as a PVC stabilizer (in the presence of HCl scavenger SCV) 2.1.3.2.1 Inorganic (mineral) compounds as SCV (Table 2)

Table 2

The results show that the effect of uncoated and coated calcium hydroxide is improved in a highly efficient manner by adding catalytic amounts of TEAP with respect to initial, middle and end stability.

Tab.2 Continued

⁴⁾ Triethanolamine perchlorato sodium (Synthesis Example 1.1.1)

⁵⁾ calcium hydroxide (uncoated)

⁶⁾ calcium hydroxide (coated with 7% Edenor L2SMGS -Fa. Cognis)

⁷⁾ hydrotalcite (ALDRICH) ⁸⁾ . Hydrotalcite (Südchemie)

It turns out that commercially available Mg-Al-Hy droxocarbonate (hydrotalcites, LDH's, anionic clays) are greatly improved in their performance by TEAP addition.

Tab.2 Continued

The findings indicate that commercially available sodium zeolite A is greatly improved in TEAP addition in its thermostabilizer effect.

Tab.2 (continued)

Here, too, a significant increase in thermal stability can be achieved by adding TEAP.

⁹⁾ Hydrotalcite (Sasol)

^9a) Dihydroxy-aluminum-sodium carbonate type A 265 (from BK Giulini)

¹⁰⁾ Na zeolite A (molecular sieve, 4A, powder <5 micron, activated - ALDRICH) ⁿ⁾ magnesium hydroxide (FLUKA)

¹²⁾ Calcium acetylacetonate (MCC)

¹³⁾ Magnesium acetylacetonate (ALDRICH) 2.1.3.2.1.1 Comparison with state of the art (SdT ¹⁴ ) - Tab.3

Table 3

A comparison of experiment 23 (CaH with sodium perchlorate) with experiment 3 (CaH with TEAP, molar base NaP) shows that when using TEAP in the tjo value, a 78%, in the t ₅₀ value, a 60% and t ₂₀₀ value is a 49% increase. Furthermore, the comparison of tests 24 and 25 (Hytal + NaP or NaZA + NaP) with Experiments 7 and 15 (Hytal + TEAP or NaZA + TEAP) shows a significant improvement in the thermostability when using TEAP as a booster.

2.1.3.2.1.2 SdT-l ¹⁶⁾

In PS - DE 10124734A1 (SdT-I) is described to apply aqueous sodium perchlorate solutions in the presence of calcium hydroxide on calcium oxide, wherein the solution water according to:

CaO + H ₂ O Ca (OH) _{2 is} ligated; This results in a solid containing as components NaClO ₄ (or NaClO _{4 *} H ₂ O) and Ca (OH) ₂ .

These substances are used as PVC thermo (co) stabilizers. In one series, the products obtained by the stated processes were combined with CaH / TEAP (1.6 / 0.16 phr), CaH-same, ClO ₄ - ( mol), the following results were obtained (Table 4).

Table 4

¹⁴⁾ general state of the art

¹⁵⁾ Sodium perchlorate monohydrate (MERCK)

¹⁶⁾ Special Prior Art 1

The PS-appropriate (SdT-1) -DHC values are averaged over several experiments. The comparison of experiment 26 with experiment 27 shows an increase of the tio, ₅₀ , ₂₀₀ values by 72%, 54% and 44 with the same total amount of stabilizer (Σ bar.) (L, 76phr) and CaH equality (1.6 phr) %. In addition, the NaP content in experiment 27 is increased by a factor of 2, which greatly increases the proportionate cost factor. A comparison of the PS-compliant SdT-I internal mixtures with non-PS-compliant external mixtures (experiment 27, 29) shows in the former (PS-according to) a worse performance. A comparison shows that in the case of CaH and NaP equality (experiment 26 versus the PS-like experiment 30) an improvement in the effect on the t ₁₀ , ₅₀ , 2 ₀₀ values by 72%, 48% and 34% takes place. Furthermore, the PVC powder samples show after end of test at the PS-compliant (SDT-I) experiments (27, 28, 29) has a significantly darker coloration, even though the thermal stress (180 ⁰ C) of the SDT samples with 279, 164 and 300 min was significantly lower than in the inventive experiment 26, which was charged over a period of 403. Likewise, the non-patent experiment 29 has a much brighter yellowing after prolonged thermal stress.

¹⁷⁾ 0.16 phr TEAP correspond to 0.072 phr NaClO ₄ x H ₂ O (C10 ₄ same)

¹⁸⁾ VP-1,2 = experimental products according to SdT PS DE 10124734A1 (Example 3) 2.1.3.2.1.3 SdT-2 ¹⁹⁾

PS-DE 10160662 A1 and DE 10214152A1 (SdT-2) claim onium (ammonium) perchlorate salts as heat (co) stabilizers. In one series, the closest compounds (SdT-2) were compared with the CaH / TEAP system according to the invention in an amount equal to the amount of charge (CaH + booster = 1.6 + 0.16 phr) (Table 5 and 6).

Tab.5

¹⁹⁾ Special Prior Art 2 Table 6

The quality factors (performance improvement) for the system according to the invention (experiment 31) compared to experiment 32 are 41%, 37% and 28%; compared to Run 33 38%, 115% and 104% and compared to Run 34 (all SdT-2) 300%, 221% and 176% with respect to the t ₁₀ , ₅₀ , ₂₀₀ values. This proves a clear superiority over SdT-2. Furthermore, the samples according to SdT-2 are more discolored after the thermal load than the samples according to the invention, although the loading times of 327, 206 and 152 min are significantly lower than with 420 min in experiment 31.

Noticeable is the moderate finding of 33 (TREHAP), which is formally similar to the TEAP (exchange of H for Na). The performance improvement is given above. Experiment 34 (TEHAP) drops even further, which is probably due to the fact that it is not an amine perchlorate but a (real) (ammonium) onium perchlorate and that the onium salt structure has an opposite (destabilizing) effect.

The amine perchlorates 31 and 32 are critical as NH perchlorates, as they are sensitive to impact and explosive. Likewise, perchloric acid is absolutely necessary for their preparation, which is subject to hazard labeling with the symbol for corrosive and the R-phrase 5-8-35. 2.1.3.2.2 Organic compounds as SCV (Tab.7 and 8)

Tab.7

It can be seen that TEAP addition to cyanguanidine results in a significant improvement in the thermal stability (t ₁₀ = 39%, t ₅₀ = 55%, t ₂₀₀ = 76%)

Tab.7 Forts.

It can be seen that the combination according to the invention of aminotriazine / TEAP (experiment 40) compared to the formulation not according to the invention (experiment 39) gives a relevant improvement boost in the thermostabilization (t ₁₀ = 196%, t ₅₀ = 230%, t ₂ oo - 308) %). It can also be seen that the combination of acetoguanamine / TEAP (experiment 42) is drastically more thermostable compared to experiment 41 (without TEAP) (t ₁₀ = 265%, I ₅₀ = 317%, t ₂ oo = 445%).

²⁰⁾ Dyhard 100SH, cyanoguanidine (dicyandiamide), fine-grained (Fa, Degussa)

²¹⁾ Cyanguanidine (dicyandiamide), normal-grained (Degussa company)

²²⁾ Melamine - normal-grained (ALDRICH)

²³⁾ melamine 003 fine-grained product (DSM)

²⁴⁾ acetoguanamine (ALDRICH) Tab.8

²⁵⁾ Bisphenol A diglycidyl ether (ALDRICH)

²⁶⁾ Bisphenol F diglycidyl ether (ALDRICH)

²⁷⁾ Bisphenol A diglycidyl ether - liquid (from Resolution)

²⁸⁾ Bisphenol A diglycidyl ether - solid (from Resolution)

²⁹⁾ hexanediol 1,6-diglycidyl ether (Grilonit RV 1812, EMS-Primid)

^29a l, 4-cyclohexanedimethanol diglycidyl ether (POLYPOX RIl, UPPC AG)

³⁰⁾ glycerol diglycidyl ether (ALDRICH)

³¹⁾ glycerol triglycidyl ether (glycidyl ether 100, ROTH)

³²⁾ Tris (2,3-epoxypropyl) isocyanurate (ALDRICH) triglycidyl isocyanurate

It can be seen that all the epoxy compounds undergo a substantial improvement in t ₁₀ values from 144% (test 46 vs. 47) to 189% (test 64 vs. 65), the t ₅₀ values of 104% (experiment 55 vs. 56) to 343% (trial 49 vs. 50) and the t ₂₀₀ - values of 108% (trial 52 vs. 53) to 312% (trial 49 vs. 50).

2.1.3.2.3 Metal soaps as SCV (Tab. 9-A)

Table 9-A

³³⁾ Lankroflex L (Akzo Nobel) - epoxidized linseed oil

³⁴⁾ Lankroflex 2307 (Akzo Nobel) - ESBO

³⁵⁾ Cardura ElOP (Fa. Resolution) - glycidyl neodecanoate

³⁶⁾ aluminum distearate (from Peter Greven Fettchemie)

³⁷⁾ Magnesium stearate (Nitika Chemicals)

³⁸⁾ calcium stearate (Nitika Chemicals)

³⁹⁾ Bäropan MC 8383 FP (Bärlocher)

⁴⁰⁾ Astab CZB (Sun Ace) As can be seen, when using commercially available stabilizer systems based on calcium / zinc soaps (mixed metals), a significant increase in activity can be achieved by addition of TEAP.

2.1.3. Effect of (A) as a PVC stabilizer (in the presence of initial color improver AFV) - Tab. 9-B

Tab. 9-B

It is clearly evident that the various initial color enhancers through TEAP addition will improve performance, with an increase in the ti, t ₅₀ and t ₂ o <r values of 88-164%, 41-160% and 43-200 % instead of.

2.1.3.4 Effect of (A) as a PVC stabilizer (in the presence of SCV + AFV) 2.1.3.4.1 Inorganic (mineral) compounds as SCV (Tab.10)

Table 10

⁴¹⁾ 1-Butylene glycol bis-S-aminocrotonate (Lonza)

⁴²⁾ Thiodiglycol-bis-3-aminocrotonate (Lonza)

In comparison to experiments without AFV and without TEAP (experiments 5 and 6), a positive influence on the thermal stability results, which is particularly pronounced in tests 91, 94, 121 and 100, 103, 106, 108 and 111.

CaH (u) and CaH (c) show in combination of AFV with TEAP compared to the trials without TEAP (87 vs. 86, 91 vs. 89, 93 vs. 92, 98 vs. 96, 100 vs. 99, 103 vs. 101, 106 vs. 105, 108 vs. 107 and 111 vs. 109) dramatically increased the tio, t ₅₀ and t ₂₀₀ values by 41-303%, 75-351% and 152-478%, respectively. The TEAP combinations show 91 vs. the same molar sodium perchlorate combinations (NaP _* H ₂ O). 90, 98

⁴³⁾ 1, 3-dimethyl-6-aminouracil ⁴⁴⁾ N-cyanoacetyl-N, N'-dimethylurea

⁴⁵⁾ 2-naphthol (ALDRICH)

⁴⁶⁾ Mono-dihydropyridine (l, 4-dihydro-2,6-dimethylpyridm-3,5-dicarboxylic acid dimethyl ester - Synthesis Example

1.2.1)

⁴⁷⁾ Mono-dihydropyridine (Stavinor ^® D507 - Arkema Fa). vs. 97, 103 vs. 102 and 111 vs. 110), which correspond to the SdT, also very significant increases of the t ₁₀ , t ₅₀ and t ₂₀ o values by 50-78%, 49-96% and 53-128

%.

Also in the Hytal system combinations of AFV with TEAP show a very significant increase of t ₁₀ compared to the trials without TEAP (113 vs. 112, 117 vs. 115, 126 vs. 124, 129 vs. 127 and 134 vs. 132), t ₅₀ and t _2O o values by 75-152%, 94-167% and 116-255%.

The TEAP combinations also show a significant increase in t ₁₀ over the possible NaP combinations (117 vs. 116, 119 vs. 118, 126 vs. 125, 129 vs. 128 and 134 vs. 133), which correspond to SdT , t ₅₀ and t ₂ oo values by 16-39%, 16-41% and 14-45%, respectively.

Tab.10 (continuation)

Also in the NaZA system, combinations of AFV with TEAP show a very marked increase in t ₁₀ , t ₅₀ and t ₂₀₀ compared to trials without TEAP (138 vs. 137, 142 vs. 140, 145 vs. 143 and 149 vs. 147) Values around 75 - 161%, 61 - 182 and 185 - 204%. The TEAP combinations show opposite to the molar NaP combinations (142 vs. 141, 145 vs. 144 and 149 vs. 148), which correspond to the SdT, also showed an increase of the t ₁₀ , t ₅₀ and t _2ö values to 28%, to 25% and to 23%.

Tab.10 (continued)

Again, the rate of increase in TE AP addition in comparison to experiments without TEAP very impressive, the rates of increase compared to NaP addition are considerable.

2.1.3.4.2 Organic compounds as HCl scavengers (Tab. 11 and 12)

Table11

Here, too, the rates of increase are present (201 vs. 199 and 201 vs. 200), they are 78%, 75% and 97% and 14% t _lo for the t ₁₀ , t ₅₀ and t _2O o values, respectively. Value.

There are also significant rates of increase (206 vs 204 and 215 vs. 213) with scores of 108-128%, 108-128% and 119-197%, as well as for 206 vs. 205 and 215 vs. 214 with values of 20 - 88%, 17 - 66% and 11 - 49%.

Hier betragen die Steigerungsraten (219 vs. 217, 223 vs. 221 und 229 vs. 227 sowie 219 vs. 218, 223 vs. 222 und 229 vs. 228) mit Steigerungsraten von 83 - 210%, 65 - 134% und 94 - 137% sowie bis 79% bis 50% und bis 32%.

Here, the rates of increase (219 vs. 217, 223 vs. 221 and 229 vs. 227 and 219 vs. 218, 223 vs. 222 and 229 vs. 228, respectively) with increases of 83-210%, 65-134% and 94% 137% as well as 79% to 50% and up to 32%.

Tab.11 (continued)

Here, the rates of increase (235 vs. 233 and 244 vs. 242 and 235 vs. 234 and 244 vs. 243) are 41-53%, 42-40% and 44-73% and up to 14%, up to 15% and up to 17 %.

Tab.11 Continued

⁴⁸⁾ N, N-diglycidylaniline (ALDRICH)

⁴⁹⁾ N, N-diglycidyl-4-glycidyloxyaniline (ALDRICH)

Here (260 vs. 258 and 264 vs. 262 and 260 vs. 259 and 264 vs. 263), the rates of increase are 103-152%, 48-109% and 47-122%, and up to 69%, up to 35% and up 10%.

Tab.11 (continued)

The positive effect with additional TEAP addition to the t _lo value can also be seen from this representation (273 vs. 272, 278 vs. 277, 280 vs. 279, 282 vs. 281, 284 vs. 283 and 290 vs.. 289).

Table 12

⁵⁰⁾ Induction time Here (293 vs. 291, 297 vs. 295, 300 vs. 298, 303 vs. 301 and 306 vs. 304 as well as 293 vs. 292, 297 vs. 296, 300 vs. 299, 303 vs. 302 and 306 vs.. 305, the rates of increase are 51% to 81%, 53% to 79% and 68% to 99%, and 14% to 40%, 15% to 39% and 20% to 39%, respectively.

Here (310 vs. 308, 314 vs. 312, 317 vs. 315, 320 vs. 318, 323 vs. 312 and 326 vs. 324) and 310 vs.. 309, 314 vs. 313, 317 vs. 316, 320 vs. 319, 323 vs. 322 and 326 vs. In 325, the rates of increase are 101 - 174%, 113 - 171% and 122 - 231%, and 11 - 70%, 9 - 46% and 10 - 36%, respectively.

⁵¹⁾ tio value 2.1.3.4.3 Other AF improvers as co-component (Tab.13)

Tab.13

Again, it can be seen that good effects can be achieved.

2.2 Performing the static heat test (SHT) 2.2.1 Production of the rolled skins

100 tees. dry mixes prepared according to the following list are added to a collin with the addition of 0.5-0.8 parts ^{57) of} a paraffin-based lubricant;

⁵²⁾ Bis-dihydropyridine (bis [l, 4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid] -l, 4-butanediol diester - Synthesis Example 1.2.2) ⁵³ 'Bis-dihydropyridine (bis- [l, 4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid] thio-diethylenglykoldiester

Synthesis Example 1.2.3)

⁵⁴⁾ Poly-dihydropyridine (poly- [1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid] -l, 4-butanediol ester - Synthesis Example 1.2.4)

⁵⁵⁾ Poly-dihydropyridine (poly [1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid thio-diethylene glycol ester]

Synthesis Example 1.2.5)

⁵⁶⁾ Hydantoin (ALDRICH)

⁵⁷⁾ Depending on the tendency to stick Labormeßwalzer ⁵⁸⁾ each plasticized at 180 ° C for 5 minutes. The resulting films (thickness 0.3 mm) are fed to further measurements.

100.0 parts Vinnolit S3160 (PVC K value = 60) 0.4 parts Initial color improver (AFV) 1.6 parts HCl scavenger (SCV) 0.16 parts TEAP (Comp. A)

2.2.2 Conduct of the test Test strips (16mm x 300mm) are cut out from the rolled skins prepared according to example 2.2.1. These are loaded in a Mathis thermal tester (type LTE, feed rate: 5 mm, basic time 5 or 45 min, cycle time 5 min) at 180 ° C. until dark discoloration (burning) occurs. Subsequently, the YI value (yellowness index) according to DIN 53381 is determined ¹²⁾ and compared with the YI value of the unloaded rolled surface (zero minute value). The results of some representative representatives are summarized in Tab. 14. The higher the YI value, the yellower (darker) the sample. The lower the YI value, the brighter the sample and the better the result.

^{58) year} : 92; Walzentemp. (vome): 182 ° C, (back): 184 ° C; Roll diameter: 150mm; Roll circumference: 0.417m; Speed - mixing: 15 [rpm] 2.2.3 Examples (Yellowness Indices-YI, Tab. 14)

Table 14

It is clear that the overall performance can be abruptly improved by TEAP addition (Comp A) instead of NaP. So are the increases in

System NaZA / DMAU / TEAP vs. NaZA / DMAU / NaP (2 vs. 4) with an initial color improvement (AFV-lOMin.) Of 147%, with an improvement in color retention (FH-30 min.) Of 199% and an increase in long-term stability (LZS -60 Min.) Of 80%. For the alternative system Mel / DMAU / TEAP vs .. NaZA / DMAU / NaP (3 vs. 4), the improvements for the AF (I OMin.) Are 242%, for the FH (30min) at 242% and for the LZ (60min.) at 36%.

System CaH (c) / DMAU / TEAP vs. NaZA / DMAU / NaP (1 vs. 4), the rates of increase for AF (lOMin) are 195%, for FH (30min) 348% and for LZ (60min) 87%.

For the also alternative system CaH (c) / mono-DHP-1 / TEAP vs.. NaZA / DMAU / NaP (6 vs. 4) show increases of 195% for AF (lOMin), 362% for FH (30min) and 37% for LZ (60min).

It shows a drastic improvement in performance.

Claims

claims 1. A composition comprising at least one synthetic polymer and at least one coordination-polymer triethanolamine-perchlorato (triflato) -metal inner complex having the monomer unit of the formula (A):

(A) where Mt = Li, Na, K, Mg, Ca, Sr, Ba and Zn; An = OClO ₃ or OS (O ₂ ) CF ₃ ; q = 1 or 2. 2. Composition according to claim 1, characterized in that it is the synthetic polymer is a halogenated polymer, preferably PVC. 3. A stabilizer system for synthetic polymers comprising a coordination polymer triethanolamine perchlorato (triflato) metal inner complex with the monomer unit of the formula (A):

(A) where Mt = Li ₃ Na, K, Mg, Ca, Sr, Ba and Zn; An = OClO ₃ or OS (O ₂ ) CF ₃ and q = 1 or 2. Stabilizer system according to claim 3, characterized in that additionally a linear and cycloureide (substituted cyanoacetylurea, substituted iminobarbituric acid, substituted aminouracil, hydantoin) and / or a 3-aminocrotonic acid ester and / or a dihydropyridine-dicarboxylic acid ester of the formula (BI) ₅ (B) 2), (CI) and (C-2).

(B-I) and (B-2) as well

(C-I) and

(C-2) with X = O or S; Y = CH ₂ CN ₅ Z = H or Y and Z form the bridge member CH ₂ - C = NH,

or R l ¹ τR> 2X _/ -. R ¹ , R ² independently of one another are H, C ₁ -C ₂₂ -alkyl, cyclohexyl, (meth) allyl, oleyl, phenyl, benzyl, phenethyl, (tetrahydro) naphthyl, meth (or eth) oxypropyl (or ethyl), CH ₂ -CHOH-R ¹³ , CH ₂ -CHOH-CH ₂ X ¹ R ^{1 a} ; X '= O or S; R = H ₅ ^la d- ₂₂ alkyl, cyclohexyl, (meth) allyl ₅ oleyl, phenyl, benzyl, phenethyl, (tetrahydro) naphthyl or meth (or eth) oxypropyl (or ethyl); R ³ = unbranched or branched C ₂ -C ₂₀ -alkylene, which may be interrupted by 1 to 4 O or S atoms and / or substituted by 1 to 4 OH groups, or dimethylol-cyclohexane-l, 4-diyl , Polyethylene (or propylene) glycol-α, ω-diyl (preferably, poly = tetra to deca), polyglyceryl-α, ω-diyl (preferably, poly = tetra to deca) or glycerol-triyl, trimethylolethane (or propane ) triyl, pentaerythritol tri (or tetra) yl, bis-trimethylolethane (or propane) tri (or tetra) yl, diglycerol tri (or tetra) yl, tetrit tetrayl, triglycerol tri (or tetra, penta) yl, pentitol pentyl, dipentaerythritol penta (or hexa) yl and hexitol hexyl; n = 2, 3, 4, 5 or 6. R ⁵ = H or (C ₃ - do-alkylidene) ^; which alkylidene may be interrupted by up to 2 O atoms or may have up to 2 substituents independently selected from the group consisting of OH, phenyl and hydroxyphenyl; R ⁶ = H, hydroxy-C ₂ - C ₄ -alkyl, 3-C ₁ - do-alkoxy-2-hydroxypropyl or mono- to trihydroxy, mono- to tri-C ₁ - C ₄ -alkyl- and / or Mono- to tri-C ₁ -C ₄ alkoxyphenyl, allyl, mono- to trisubstituted phenyl; R ⁷ , R ^{7 'are} independently branched and unbranched C ₁ -C ₄ -alkyl, Phenyl, cyclohexyl; W = CO ₂ CH ₃ , CO ₂ C ₂ H ₅ , CO ₂ ¹¹ C ₁₂ H ₂₅ or CO ₂ C ₂ H ₄ -S- ¹¹ C ₁₂ H ₂₅ ; L, T = unsubstituted C _1-12 alkyl; and m and n ^{f are} integers from 0 to 20, k is O or 1 and R and ^{RΛ are} independently ethylene, propylene, butylene or an alkylene or cycloalkylene bismethylene group of the type - (C _p H _2p -X "-) _t CpH _2p -, where p is an integer from 2 to 8, t is an integer Number is from 0 to 10 and X "is oxygen or sulfur. 5. stabilizer system according to claim 3 or 4, characterized in that additionally magnesium or calcium oxide or hydroxide and / or a magnesium or calcium soap and / or a Ca / Zn stabilizer and / or a (optionally Li or titanium-containing ) Hydrotalcite and / or dawsonite and / or sodium zeolite A and / or a Ca-Al-hydroxo-hydrogen phosphite and / or a glycidyl compound and / or an epoxidized fatty acid ester and / or a melamine and / or a phosphorous acid ester and / or 2-naphthol and or a cyanamide of the formula (E)

(E) where each R ⁴ independently of one another = H, nitrile, carbamoyl, R ¹ , R ² , R ¹ CO, 1 A R is CO, Na, K, Mg _1Z2 and Ca _1Z2 or R ₂ = tetra-, penta- or hexamethylene and o = 1, 2 or 3 is added. 6. Stabilizer system according to one of claims 3 to 5, characterized in that a sterically hindered amine (HALS) and / or an antioxidant and / or a UV absorber (Benzotriazolderivat) and / or titanium dioxide and / or chalk is added. 7. Stabilizer system according to claim 6, characterized in that the sterically hindered amine (HALS) is a NOR-HALS compound. 8. Stabilizer system according to claim 7, characterized in that the NOR-HALS compound is a triazine-based NOR-HALS compound. 9. stabilizer system according to one of claims 3 to 8, characterized in that it further comprises a glycerol ether and / or ester, R ⁸ OCH ₂ CH (OH) CH ₂ OH or R ⁸ CO ₂ CH ₂ CH (OH) CH ₂ OH and / or a DEA derivative R ⁹ - [C (O)] _d -N (C ₂ H ₄ θH) ₂ or R ⁸ OCH ₂ CH (OH) CH ₂ - [C (O)] _C IN (C ₂ H ₄ OH) ₂ or R ⁹ -N (OH) (CH ₂ ) ₂ (CH ₂ ) ₃ - [C (O)] _d - N (C ₂ H ₄ OH) ₂ and / or a paraffin sulfate (or sulfonate ) Salt C ₁₂ -C ₁₈ -alkyl- (O) _d -SO ₃ Na, Li, K and / or a polyoxyalkylene of the formula (F) R ^{8 is} -O- [CH (R ¹⁰ ) -CH ₂ -O-] _a - [CH ₂ - [CH (OH)] _b --CH ₂ -O] _c - [C (O)] _{d "} - R ⁹ (F) in which Each R ⁸ irrespectively = H, C ₁ -C ₂₄ alkyl, C ₂ - C ₂₄ alkenyl, CH ₂ = CH-C (O) or CH ₂ = CCH ₃ -C (O); Each R ⁹ independently = C ₁ -C ₂₄ alkyl, C ₂ - C ₂₄ alkenyl, (CH _{2) 2} OH, CH ₂ -COOH or N (C ₁ - C ₈ alkyl) ₃ Hal, R ¹⁰ = H or CH ₃ , Hal = Cl, Br or I; a = an integer greater than or equal to 2, b = an integer from 1 to 6, and c, d, d ', d "independently = O or contains 1. 10. A composition comprising a synthetic polymer and a stabilizer system according to any one of claims 4 to 9. 11. The composition according to claim 10, characterized in that the synthetic polymer is a chlorine-containing polymer, preferably PVC. 12. The composition according to claim 11, characterized in that the chlorine-containing polymer is hard, soft, suspension or emulsion PVC. 13. The composition according to any one of claims 10 to 12, characterized in that based on 100 parts by wt. Of synthetic polymer 0.001-1.0 parts by wt. Of the inner complex (A) are included. 14. A composition according to any one of claims 10 to 13, characterized in that 0.01-10 parts by weight of hindered amine and / or NOR-HALS Compound and / or UV absorber and / or titanium dioxide are included. Composition according to any one of Claims 10 to 14, characterized in that the synthetic polymer comprises plasticized PVC and the stabilizer system contains 1,4-cyclohexanedimethanol diglycidyl ether. 16. A process for the stabilization of synthetic polymers by adding a stabilizer system according to any one of claims 5 to 10 to a synthetic polymer. 17. A method for stabilizing synthetic polymers according to claim 16, characterized in that the synthetic polymer is a chlorine-containing polymer, preferably plasticized PVC or paste PVC. 18. A process for the stabilization of chlorine-containing polymers according to claim 17, characterized in that the soft PVC is suitable for the production of floors, automotive parts, wall-mounted wallpaper, flexible films, hoses, injection molded parts or preferably for wire sheathing (cable). 19. A process for the stabilization of synthetic polymers according to claim 17, characterized in that the chlorine-containing polymer is hard PVC. 20. A method for stabilizing chlorine-containing polymers according to claim 19, characterized in that the rigid PVC is suitable for the production of films (including Luvitherm), PVC pipes or profiles, preferably of window profiles. 21. Utility articles containing PVC, which also contain a stabilizer system according to one of claims 5 to 10. An antistatic or antistatic component for synthetic polymers comprising a triethanolamine perchlorato (triflato) metal inner complex of the formula (A) as defined in claim 1. 23. Inner complex of the formula (A) as specified in claim 1, characterized in that Mt = Ca or Zn and q = 2. 24. Inner complex of formula (A) as set forth in claim 1, wherein Mt = Li, Na or Ca and q = 1 or 2. 25. Inner complexes according to claim 24, characterized in that Mt = Li or Na, q = 1 and An = OClO ₃ . 26. A process for preparing an inner complex of the formula (A) as specified in claim 1, characterized in that the synthesis is carried out in methanol, ethanol, propanol, triethanolamine or water and the solvent and any water of reaction are removed by distillation. 27. The method according to claim 26, characterized in that the distillation residue is digested in a non-polar solvent. 28. A process for the preparation of inner complexes of the formula (A) as specified in claim 1, characterized in that the synthesis is carried out in an alcohol and the reaction product is separated by precipitation with a non-polar solvent.